Catalyst and method of preparing light olefin directly from synthesis gas by one-step process

Abstract

The present invention discloses catalyst and method for producing light olefins directly from synthesis gas by a one-step process, and particularly relates to method and catalyst for directly converting synthesis gas into light olefins by a one-step process. The provided catalysts are composite materials formed of multicomponent metal oxide composites and inorganic solid acids with hierarchical pore structures. The inorganic solid acids have a hierarchical pore structure having micropores, mesopores and macropores. The metal composites can be mixed with or dispersed on surfaces or in pore channels of the inorganic solid acid and can catalyze the synthesis gas conversion to a C.sub.2-C.sub.4 light hydrocarbon product containing two to four carbon atoms. The single pass conversion of CO is 10%-60%. The selectivity of light hydrocarbon in all hydrocarbon products can be up to 60%-95%, wherein the selectivity of light olefins (C.sub.2.sup.C.sub.4.sup.) is 50%-85%.

Claims

1. A catalyst, comprising a multicomponent metal composite dispersed on surfaces or in pore channels of an inorganic solid acid, wherein the multicomponent metal composite comprises two or more metals, and a weight percentage of the multicomponent metal composite in the catalyst is 10 wt % to 75 wt %, wherein the inorganic solid acid has a hierarchial pore structure and comprises micropores having pore diameters of less than 2 nm, mesopores having pore diameters of 2 nm to 50 nm, and macropores having pore diameters of larger than 50 nm, wherein the inorganic solid acid support has a BET surface area of 100-1200 m.sup.2/g, and a pore volume of 0.25-0.80 ml/g, determined by N2 physical adsorption, and wherein 16-68% of the BET surface area is attributed to the micropores, 17-57% of the BET surface area is attributed to the mesopores, and 10-32% of the BET surface area is attributed to the macropores.

2. The catalyst according to claim 1, wherein each of the two or more metals in the multicomponent metal composite is in a form independently selected from the group consisting of a metal oxide, an elemental metal, a metal carbide, a metal nitride, and a metal inorganic salt, and wherein the two more metal elements comprises one or more necessary metal element and one or more other element, wherein the one or more necessary metal element is selected from the group consisting of Zn, Co, Cr, and Mn, wherein a molar ratio of the one or more necessary element to the one or more other element is (0.1-5.0):1, wherein the metal inorganic acid salt comprises a cation and an anion, wherein the metal in the cation is selected from the group consisting of Li, Na, Mg, Al, K, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga, Ge, Zr, Mo, Pd, Ag, Cd, Sn, Cs, and Ce, and the anion is selected from the group consisting of ZnO.sub.2.sup.2, Al.sub.2O.sub.4.sup.2, SiO.sub.3.sup.2, SiO.sub.4.sup.4, TiO.sub.3.sup.2, TiO.sub.3.sup.3, VO.sub.3.sup., VO.sub.3.sup.2, CrO.sub.4.sup.2, Cr.sub.2O.sub.4.sup.2, Mn.sub.2O.sub.4.sup.2, Fe.sub.2O.sub.4.sup.2, Co.sub.2O.sub.4.sup.2, Ni.sub.2O.sub.4.sup.2, Fe(CN).sub.6.sup.3, Fe(CN).sub.6.sup.4, MoO.sub.4.sup.2, TiO.sub.3.sup.2, ZrO.sub.3.sup.2, CeO.sub.3.sup.2, Ga.sub.2O.sub.4.sup.2, In.sub.2O.sub.4.sup.2, GeO.sub.3O.sup.2, GeO.sub.4.sup.4, and SrO.sub.3.sup.4and wherein the metal in the cation and the metal in the anion are not the same.

3. The catalyst according to claim 2, wherein the multicomponent metal composite comprises secondary particles of 10 nm-200 m in size and having mesopores of 2-20 nm in diameter, and wherein the secondary particles comprises crystal particles of 0.5-20 nm aggregated together.

4. The catalyst according to claim 1, wherein the inorganic solid acid is composed of Si, O, and H, is composed of Si, Al, O, and H, is composed of Si, Al, P, O, and H, is composed of Ti, Si, O, and H, is composed of Zr, Si, O, and H, is composed of Ge, Si, O and H, or is composed of Ge, Al, P, O and H.

5. The catalyst according to claim 1, wherein the inorganic solid acid comprises weak acid sites, medium strong acid sites, and strong acid sites defined according to NH.sub.3-TPD (temperature programmed desorption), wherein the weak acid sites have a deposition temperature of NH.sub.3 lower than 275 C., the medium strong acid sites have a deposition temperature of NH.sub.3 between 275 C. and 500 C., and the strong acid sites have a deposition temperature of NH.sub.3 higher than 500 C., wherein an amount of the medium strong acid sites is 0.06-10 mol/kg.

6. A method for preparing light olefins directly from a synthesis gas using the catalyst of claim 1, comprising: contacting the synthesis gas with the catalyst of claim 1 in a reactor, wherein a volume ratio of H.sub.2/CO in the synthesis gas is 0.5-4.

7. The method according to claim 6, further comprising pretreating the catalyst in a gas mixture at 250-600 C. under a pressure of 0.1-3.0 MPa at a space velocity of the gas mixture of is 500-5000 h.sup.1, wherein the gas mixture is a mixture of hydrogen and carbon monoxide at a volume ratio of H.sub.2/CO between 0.5-4; or a mixture of hydrogen and inert gas selected from the group consisting of nitrogen, helium, argon, neon, or mixtures thereof, and a volume percentage of hydrogen in the mixture is 5-100%; or a mixture of carbon monoxide and inert gas selected from the group consisting of nitrogen, helium, argon, neon, or mixtures thereof, and a volume percentage of carbon monoxide in the mixture is 5-100%.

8. The method according to claim 6, wherein the synthesis gas comprises H.sub.2, CO, and one or more selected from the group consisting of an inert gas and an non-inert gas, wherein the inert gas is one or more selected from the group consisting of nitrogen, helium, argon, and neon, wherein the non-inert gas is one or more selected from the group consisting of carbon dioxide, steam, methanol, and ethanol, and wherein the volume percentage of the inert gas in the synthesis gas is less than 10% and the volume percentage of the non-inert gas in the synthesis gas is less than 50%.

9. The method according to claim 6, wherein the reactor is a fluidized bed, a moving bed, or a fixed bed, wherein a reaction temperature is 300-500 C., and a space velocity of the synthesis gas is 500-10000 h.sup.1 .

10. The catalyst according to claim 2, wherein the necessary metal element is Zn, and the other element is one or more selected from the group consisting of Li, Na, Mg, Al, K, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Co, Cu, Ga, Ge, Zr, Mo, Pd, Ag, Cd, In, Sn, Cs, La, and Ce.

11. The catalyst according to claim 10, wherein the other element is one or more selected from the group consisting of Al, Ti, Cr, Mn, Co, Cu, Pd, and Ce.

12. The catalyst according to claim 2, wherein the necessary metal element is Co, and the other element is one or more selected from the group consisting of Li, Na, Mg, Al, K, Ca, Sr, Ba, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge, Zr, Mo, Pd, Ag, Cd, In, Sn, Cs, La, and Ce.

13. The catalyst according to claim 12, wherein the other element is one or more selected from the group consisting of Al, Ti, Cr, Mn, Cu, Zn, Pd, and Ce.

14. The catalyst according to claim 2, wherein the necessary metal element is Cr, and the other element is one or more selected from the group consisting of Li, Na, Mg, Al, K, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Cu, Zn, Ga, Ge, Zr, Mo, Pd, Ag, Cd, In, Sn, Cs, La, and Ce.

15. The catalyst according to claim 14, wherein the other element is one or more selected from the group consisting of Al, Ti, Mn, Co, Cu, Zn, Pd, and Ce.

16. The catalyst according to claim 2, wherein the necessary metal element is Mn, and the other element is one or more selected from the group consisting of Li, Na, Mg, Al, K, Ca, Sr, Ba, Ti, Cr, Fe, Co, Cu, Zn, Ga, Ge, Zr, Mo, Pd, Ag, Cd, In, Sn, Cs, La, and Ce.

17. The catalyst according to claim 16, wherein the other element is one or more selected from the group consisting of Al, Ti, Cr, Co, Cu, Zn, Pd, and Ce.

18. A catalyst, comprising a multicomponent metal composite dispersed on surfaces or in pore channels of an inorganic solid acid, wherein the muiticomponent metal composite comprises two or more metals, and a weight percentage of the multicomponent metal composite in the catalyst is 10 wt % to 75 wt %, wherein the inorganic solid add has a hierarchical pore structure and comprises micropores having pore diameters of less than 2 nm, mesopores having pore diameters of 2 nm to 50 nm, and macropores having pore diameters of larger than 50 nm, wherein the inorganic solid add has a BET surface area of 100-1200 m.sup.2/g, and a pore volume of 0.25-0.80 ml/g, determined by N2 physical adsorption, and wherein 10-65% of the BET surface area is attributed to the micropores, 20-75% of the BET surface area is attributed to the mesopores, and 15-70% of the BET surface area is attributed to the micropores macropores.

19. The catalyst according to claim 18, wherein the inorganic solid acid has a BET surface area of 100-1200 m.sup.2/g, and a pore volume of 0.25-0.80 ml/g, determined by N2 physical adsorption, and wherein 10-50% of the BET surface area is attributed to micropores, 30-70% of the BET surface area is attributed to mesopores, and 20-60% of the BET surface is attributed to macropores.

Description

DESCRIPTION OF DRAWINGS

(1) FIG. 1 is an SEM picture of Cu.sub.1Zn.sub.1@SiAl of a core-shell structure in embodiment 8;

(2) FIG. 2 is an XRD graph of Cu.sub.1Zn.sub.1@SiAl in embodiment 8;

(3) FIG. 3 is an N.sub.2 physical adsorption curve and a pore diameter distribution diagram of silicon-phosphorus-aluminum inorganic solid acid with a hierarchical pore structure in embodiment 14; and

(4) FIG. 4 is a chromatogram of the on-line chromatographic analysis of direct conversion of synthesis gas into products in embodiment 6.

DETAILED DESCRIPTION

(5) The present invention is further illustrated below by the embodiments, but the scope of claims of the present invention is not limited by the embodiments. Meanwhile, the embodiments only give some conditions for achieving the purpose, but it doesn't mean that the conditions must be satisfied to achieve the purpose.

(6) Example of Catalytic Reactions

(7) A continuous flow fixed bed reaction is taken as an example, but the catalyst is also applicable to a fluidized bed reactor. The apparatus is equipped with gas mass flow meters, gas deoxidization and dehydration tubes, and online product analysis chromatography (the tail gas of the reactor is directly connected with the metering valve of chromatography, and thus periodic and real-time sampling and analysis will be achieved). Before use, the above catalyst is compressed and sieved into particles of 20-40 meshes or 40-60 meshes for later use.

(8) 2.8 g of catalyst in the following embodiments or reference examples is placed in a fixed bed reactor. The air in the reactor is replaced with Ar; and then reduction is conducted in a pure H.sub.2 atmosphere at 310 C.-350 C. for 1 h. The temperature is cooled to room temperature in the Ar atmosphere, and then the Ar atmosphere is switched to synthesis gas (5% Ar; H.sub.2/CO=2/1). The temperature is raised to reaction temperature, and the air velocity and the pressure of the reaction raw gas are regulated. The on-line chromatography is used to detect and analyze the product. The reaction performance can be changed by changing the temperature, pressure, space velocity and H.sub.2/CO ratio.

(9) Embodiment 1

(10) A composite catalyst of the multicomponent metal composite and the inorganic solid acid with a hierarchical pore structure is prepared by a chemical compounding method.

(11) The multicomponent metal composite of CuZnAl and silicon-aluminum inorganic solid acid with a hierarchical pore structure are taken as examples.

(12) The raw materials of 30% silica sol (mass concentration), aluminum sulfate, sodium hydroxide, N,N,N-trimethyl-adamantane ammonium hydroxide (R) and deionized water are weighed according to the oxide SiO:Al.sub.2O.sub.3:Na.sub.2O:R.sub.2O:H.sub.2O=40:1:16:5:900 (mass ratio); after mixing at room temperature and stirring at 60 C. and 200 rpm for 24 h, the mixture is transferred to a hydrothermal reactor and crystallized at 155 C. for 6 d. The mixture is naturally cooled to room temperature and transferred to a beaker to have a water bath at 70 C. Ammonium chloride is added according to a ratio of 100 ml of stock solution to 4 g of ammonium chloride, stirred at constant temperature for 3 h and subjected to centrifugal washing repeatedly so that the pH of the supernatant is 7 at the end of washing. After the precipitate is dried at 120 C. for 24 h, the precipitate is calcined in air at 650 C. for 3 h to obtain the silicon-aluminum inorganic solid acid with hierarchical pore structure.

(13) 5.3 g of the prepared silicon-aluminum inorganic solid acid with hierarchical pore structure is weighed; 1.2 g of copper nitrate trihydrate, 1.49 g of zinc nitrate hexahydrate and 1.8 g of aluminum nitrate nonahydrate are taken and dissolved into 100 ml of aqueous solution; CuZnAl is introduced into the silicon-aluminum inorganic solid acid with hierarchical pore structure through an immersion method, dried in vacuum at room temperature and calcined in still air at 500 C. for 1 h to obtain Cu.sub.1Zn.sub.1Al.sub.1/mesoSiAl with a mole ratio of elements of 1:1:1. The loading capacity of the multicomponent metal composite is 20 wt %. According to the method, the metal components and the proportions thereof as well as the loading capacity of the multicomponent metal composite can be changed.

(14) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 347 m.sup.2/g with micropore size distribution of 3-4 , and the mesoporous specific surface area is 214 m.sup.2/g with mesopore size distribution of 2-15 nm, and the macroporous specific surface area is 62 m.sup.2/g.

(15) X-ray diffraction (XRD) shows that the multicomponent metal composite contains CuO, ZnO, Al.sub.2O.sub.3, ZnAlO.sub.2 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 5-15 nm and the crystal size of the inorganic solid acid is 40-70 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid with hierarchical pore structure is 10-100 m and the crystal size of the inorganic solid acid is 10-100 nm. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 5-15 nm and the secondary particle size is 15-50 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 360 C., and the amount of sites of the medium strong acid is 2 mol/kg. The medium strong acid is defined according to NH.sub.3-TPD and is the position of a desorption peak according to NH.sub.3. The position of the desorption peak means that under standard test conditions that a ratio of sample mass w and carrier gas flow rate f is 100 g.Math.h/L and a heating rate is 10 C./min, a TCD records a thermal conductivity signal of desorption of NH3 and draws a desorption curve; according to peaks in positions of curve peaks, the inorganic solid is divided into three acid intensities. The medium strong acid is an acid site where the deposition temperature of NH.sub.3 is between 275 C. and 500 C.

(16) Embodiment 2

(17) The preparation process is substantially the same as that of embodiment 1, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with a hierarchical pore structure in embodiment 1, the crystallization temperature is changed to 150 C. for 5 days to prepare the silicon-aluminum inorganic solid acid of CHA topology with the amount of sites of the medium strong acid of 0.8 mol/kg.

(18) In the reference example 1, the preparation process is substantially the same as that of embodiment 1, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure in embodiment 1, the crystallization temperature is changed to 140 C. for 3 days to prepare the silicon-aluminum inorganic solid acid with the amount of sites of the medium strong acid of 0.01 mol/kg.

(19) In the reference example 2, the preparation process is substantially the same as that of embodiment 1, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure in embodiment 1, the crystallization temperature is changed to 140 C. for 22 h to prepare the silicon-aluminum inorganic solid acid with the amount of sites of the medium strong acid of 0.005 mol/kg.

(20) Under reaction conditions of 365 C., 2 MPa and volume space velocity of 4000 h.sup.1, reaction results are shown in the table below.

(21) TABLE-US-00002 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ Conversion Selectivity Selectivity Hydrocarbon Olefin Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 1 15.63 54.56 1.71 88.77 50.56 9.52 Embodiment 2 6.14 55.80 5.96 79.41 50.27 14.63 Reference 2.33 70.39 37.63 34.17 13.79 28.20 Example 1 Reference 1.28 68.17 41.29 45.62 11.08 13.09 Example 2

(22) The CO conversion in the reference examples 1 and 2 are very low because of the low amount of the sites of the medium strong acid in the solid acid, resulting in that the intermediate species generated on the multicomponent metal composite cannot be timely and well converted into the target product. Meanwhile, methane selectivity is increased greatly to be more than 30%, while the selectivity of the light olefins is also reduced significantly. In contrast, the CO conversion of the catalyst containing more medium strong acid in the present invention is greatly increased, and the selectivity of the target product olefins is also high. The CO conversion in embodiment 1 is significantly higher than that in embodiment 2 because the catalyst is within the preferred range. It can be seen that the acid content of the silicon-aluminum inorganic solid acid with hierarchical pore structure is extremely important for the control of the catalytic properties including the CO conversion and the selectivity.

(23) Embodiment 3

(24) A composite catalyst of the multicomponent metal composite and the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is prepared by a chemical compounding method.

(25) The raw materials of 30% silica sol (mass concentration), aluminum sulfate, phosphoric acid, TEA (R) and deionized water are weighed according to the oxide SiO:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O=18:16:32:55:150 (mass ratio); after mixing at room temperature, stirring and aging at 30 C. and stirring at 500 rpm for 72 h, the mixture is transferred to a hydrothermal reactor and crystallized at 220 C. for 15 h. The water bath is quenched to room temperature. Centrifugal washing is conducted repeatedly so that the pH of the supernatant is 7 at the end of washing. After the precipitate is dried at 130 C. for 17 h, the precipitate is calcined in air at 580 C. for 5 h to obtain the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure.

(26) 2.1 g of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is weighed; 1.54 g of zinc nitrate hexahydrate and 3.8 g of aluminum nitrate nonahydrate are taken and dissolved into an aqueous solution to prepare a mixed solution A; 6.3 g of ammonium carbonate is weighed and dissolved in 100 ml of water to prepare a solution B; the solution B is dropwise added at 50 C. to the mixed solution A stirred at a power of 7 W with tip ultransonic and a speed of 400 rpm; centrifugal washing is conducted so that the pH of the supernatant is 7 at the end of washing; the mixture is dried in the air at 110 C. and calcined in still air at 500 C. for 2 h to obtain ZnCr.sub.1.8/SiPAl. Then, through ZnCr.sub.1.8/SiPAl as a carrier, 0.057 g of palladium diacetate Pd(Ac).sub.2 is accurately weighed and dissolved in acetone, and introduced into ZnCr.sub.1.8/SiPAl by impregnation, wherein the mole ratio of Pd to Zn is 0.01. Pd.sub.0.01ZnCr.sub.1.8/SiPAl with the element mole ratio of 0.01:1:1.8 is obtained. The loading capacity of the multicomponent metal composite is 20 wt %. According to the method, the metal components and the proportions thereof as well as the loading capacity of the multicomponent metal composite can be changed.

(27) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is in the range of 4-5 , while mesopore size distribution in 2-8 nm. The total specific surface area is 416 m.sup.2/g, with 35% of the mesoporous specific surface area and 20% of the macroporous specific surface area. X-ray diffraction (XRD) shows that the multicomponent metal composite contains Cr.sub.2O.sub.3, CrO.sub.3, ZnO, Al.sub.2O.sub.3, ZnCr.sub.2O.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, and the crystal size of the metal oxide and the crystal size of the inorganic solid acid are 7-16 nm and 50-60 nm, respectively. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 100-500 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 7-16 nm and the secondary particle size is 20-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 386 C., and the amount of sites of the medium strong acid is 6 mol/kg.

(28) Embodiment 4

(29) The preparation process is substantially the same as that of embodiment 3, and the difference is that in preparation of the silicon-aluminum inorganic solid acid, the stirring time is changed to 3 h, and the crystallization time is changed to 24 h to prepare the silicon-aluminum inorganic solid acid of CHA topology, with the total specific surface area of 377 m.sup.2/g, including 21% of mesoporous specific surface area and 20% of macroporous specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 385 C., and the amount of sites of the medium strong acid is 5.8 mol/kg.

(30) In the reference example 3, the preparation process is substantially the same as that of embodiment 3, and the difference is that in preparation of the silicon-aluminum inorganic solid acid, the aging temperature is changed to 80 C., and the crystallization is conducted at 240 C. for 24 h after stirring for 2 d to obtain the silicon-aluminum inorganic solid acid of CHA topology, with the total specific surface area of 232 m.sup.2/g, including 4% of mesoporous specific surface area and 1% of macroporous specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 411 C., and the amount of sites of the medium strong acid is 2 mol/kg.

(31) In the reference example 4, the preparation process is substantially the same as that of embodiment 3, and the difference is that in preparation of the silicon-aluminum inorganic solid acid, the aging temperature is changed to 30 C., and the crystallization is conducted at 240 C. for 48 h after stirring for 2 d to obtain the silicon-aluminum inorganic solid acid of CHA topology, with the total specific surface area of 287 m.sup.2/g, including 10% of mesoporous specific surface area and 4% of macroporous specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 390 C., and the amount of sites of the medium strong acid is 5 mol/kg.

(32) In the reference example 5, the preparation process is substantially the same as that of embodiment 3, and the difference is that in preparation of the silicon-aluminum inorganic solid acid, through calculation by the specific surface area, a commercial SBA-15 molecular sieve with mesopore size distribution of 4-8 nm is mechanically mixed with the silicon-aluminum inorganic solid acid in the reference example 3; the mixing ratio is 13:7 in terms of the specific surface area of the silicon-aluminum inorganic solid acid to SBA-15; and then the mixture is ground and mixed to obtain the silicon-aluminum inorganic solid acid having mesoporous and microporous composite, wherein the proportions of microporous, mesoporous and macroporous specific surface areas in total specific surface area are 62%, 36% and 2% respectively. But the mesopore channels with diameters of 2-50 nm are not formed by stacking inorganic solid acid crystal particles, wherein the primary pores are not located in pore walls of adjacent secondary pores and/or tertiary pores, but the primary pores exist alone, while the secondary and tertiary pore channels also exist alone. The three kinds of pore channels not in conformity with the claims are mutually connected and do not constitute a three-dimensional hierarchical pore channel structure.

(33) Under reaction conditions of 400 C., 2.5 MPa and volume space velocity of 4000 h.sup.1, reaction results are shown in the table below.

(34) TABLE-US-00003 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ Conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % Embodiment 3 22.78 59.35 1.64 95.66 80.04 2.7 Embodiment 4 20.11 58.09 4.90 85.16 60.57 9.94 Reference Example 13.83 57.90 10.84 77.93 5.77 11.23 Reference Example 17.36 59.26 6.28 86.99 25.74 6.73 Reference Example 13.55 54.28 11.73 79.64 8.02 8.63
The selectivity of the light olefins in embodiment 3 is significantly better than that in reference examples 3 and 4, and even better than that in embodiment 4 because in embodiment 3, the proportions of the mesoporous specific surface area to and the macroporous specific surface area to total specific surface area of the silicon-aluminum inorganic solid acid are 35% is 20% and are within a more preferred range compared with the proportions of the mesoporous specific surface area and the macroporous specific surface area to total specific surface area: 21% and 20% in embodiment 4. Therefore, the mass transfer is better, thereby inhibiting the production of alkanes from hydrogenation, and increasing the selectivity greatly. However, the selectivity of the light olefins in the reference example is far below the selectivity of the catalyst of the present invention because the number of mesopores and macropores of the molecular sieve is too small and fail to reach the content of the mesopores and the macropores in claims. Therefore, mass transfer is not convenient. Meanwhile, the change of acid intensity causes excessive hydrogenation in the product to produce alkane, thereby greatly reducing the selectivity of the light olefins. In the reference example 5, although the content of the mesopores and the macropores conform to the ranges in claims, three kinds of contained pore channels are not mutually connected and communicated, and do not form the three-dimensional three-level pore channel structure in claims. In addition, the medium strong acid on the surface and in the pore channels of SBA-15 is little. Therefore, the medium strong acid in the reference example 5 is mainly distributed in the micropores, instead of being uniformly distributed in the three-dimensional three-level pore channels inconsistent with claim 5. Thus, no substantial change is made compared with the reference example 3, and the selectivity of the light olefins is still very low. In contrast, for catalyst with the three-dimensional hierarchical pore channel structure having 20-75% of mesoporous specific surface area and 20-65% of macroporous specific surface area, the selectivity of olefins is greater than 60%, which is not only much higher than that of the reference examples 3 and 4, but also higher than the theoretical selectivity 58% of light olefins of traditional Fischer-Tropsch synthesis. It can be seen that the pore channel structure of the inorganic acid is extremely important for the control of the product selectivity.

(35) Embodiment 5

(36) Preparation of a composite catalyst of multicomponent metal composite and silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure through a physical compounding method. The method comprises mixing different materials by means of ball milling, mechanical mixing instrument, shaker, oscillation shocker mixing and the like.

(37) The silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure: the crosslinking agent of triethylamine, gelatin and glutaraldehyde is used as a template. 10 g of aluminum isopropoxide, 5.30 g of strong phosphoric acid, 3.67 g of silica sol (a mass concentration of 30%), 1.46 g of triethylamine and 13.2 g of H.sub.2O are mixed and stirred at room temperature for 3 h at a stirring speed of 400 rpm. Then 1.68 g of 2 wt % gelatin solution is added, heated to 57 C. and continuously stirred for 0.5 h. The obtained mixed solution is poured into a culture dish and frozen at 0 C. for 12 h to obtain gel. An appropriate amount of 5 wt % glutaraldehyde is added to have a crosslinking reaction. The suspension after the reaction is centrifuged at 10000 rpm. The obtained solid sample is dried in a 50 C. oven overnight and then filled in a Teflon liner. The small Teflon liner is placed in a larger Teflon liner to which an appropriate amount of the mixed solution of triethylamine and water is added in advance. Then, the larger and the smaller liners are filled together into a stainless steel self-pressure crystallization kettle, crystallized at 200 C. through a dry gum method for 36 h, and subjected to repeated centrifugal washing so that pH of the supernatant is 7 at the end of washing. The precipitate is dried at 90 C. for 6 h, and calcined in air at 550 C. for 3 h after drying at 110 C. for 12 h to obtain the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure.

(38) 17.33 g of zinc nitrate hexahydrate and corresponding amount of copper nitrate hexahydrate, cobalt nitrate hexahydrate and chromium nitrate nonahydrate are respectively weighed according to a molar ratio of the metal elements Zn:Cu:Co:Cr:Al of 6:0.2:1:1:1 and dissolved in 100 ml of deionized water. YAl.sub.2O.sub.3 is added and subjected to ultrasonic agitation at 25 C., with the tip ultrasonic power of 5 W and stirring speed of 300 rpm. Then, the mixture is dried in air at 110 C. and calcined at 500 C. to obtain the multicomponent metal composite Zn.sub.6Cu.sub.0.2Co.sub.1Cr.sub.1Al.sub.1 with element molar ratio of 6:0.2:1:1:1.2 g of the multicomponent metal composite and 5 g of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure are placed in Teflon mixing tank. The air is replaced three times by helium at first, and then 2% H.sub.2 (He balance) is introduced into the tank. The mixing tank is then closed and mixed at a rate of 450 rpm for 5 minutes to prepare the composite catalysts Zn.sub.6Cu.sub.0.2Co.sub.1CrAl/SiPAl, wherein the multicomponent metal composite accounts for 40 wt % of the total mass of the catalyst. In this way, the content of the multicomponent metal composite and the kind of the inorganic solid acid with hierarchical pore structure can be changed.

(39) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 243 m.sup.2/g with micropore size distribution of 4-5 , the mesoporous specific surface area is 318 m.sup.2/g with mesopore size distribution of 15-25 nm, and the macroporous specific surface area is 182 m.sup.2/g. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 367 C., and the amount of sites of the medium strong acid is 1.5 mol/kg.

(40) In embodiment 6, the preparation process is substantially the same as that of embodiment 5, and the difference is that content of the multicomponent metal composite is adjusted to 15 wt %, based on 100% of the total mass of the catalyst.

(41) In reference example 6, the preparation process is substantially the same as that of embodiment 5, and the difference is that content of the multicomponent metal composite is adjusted to 5 wt %, based on 100% of the total mass of the catalyst.

(42) In reference example 7, the preparation process is substantially the same as that of embodiment 5, and the difference is that content of the multicomponent metal composite is adjusted to 90 wt %, based on 100% of the total mass of the catalyst.

(43) Embodiment 7

(44) The preparation process is substantially the same as that of embodiment 5, and the difference is that in preparation of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure, the crystallization temperature is changed to 190 C., the time is 33 h; and calcination temperature is 600 C. and the time is 3 h. The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure, with the micropore size distribution of 10-15 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 10-70 m and the crystal size of the inorganic solid acid is 60-80 nm. NH.sub.3 desorption peak temperature of medium strong acid is 385 C., and the amount of sites of the medium strong acid is 1.5 mol/kg.

(45) In reference example 8, the preparation process is substantially the same as that of embodiment 7, and the difference is that in preparation of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure, the crystallization temperature is changed to 160 C., the time is 24 h; and calcination temperature is 550 C. and the time is 8 h. Calcination is conducted under flowing air. The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure, with the mesopore size distribution of 2-5 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 5-100 nm and XRD shows that the crystal size of the inorganic solid acid is 1-5 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 349 C., and the amount of sites of the medium strong acid is 0.06 mol/kg.

(46) Under reaction conditions of 370 C., 2 MPa and volume space velocity of 6000 h.sup.1, reaction results are shown in the table below.

(47) TABLE-US-00004 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ Conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 5 6.67 54.88 3.04 82.91 62.11 14.05 Embodiment 6 4.17 55.34 3.29 83.66 56.77 13.05 Reference Example 6 3.30 62.17 70.71 20.56 10.38 8.73 Reference Example 7 1.22 53.03 5.74 50.64 46.11 43.62 Embodiment 7 13.78 62.72 2.97 86.03 66.84 11.00 Reference Example 8 2.58 27.38 44.69 47.90 28.15 7.41

(48) The CO conversion in reference examples 6 and 7 are far below the CO conversion in embodiments. The methane selectivity in reference example 6 is as high as 70%, while the selectivity of C.sub.5+ in reference example 7 exceeds 40% and the selectivity of light olefins is also lower than the result of the catalyst in the present invention because the content of the proportional multicomponent metal composite in the entire catalyst does not conform to the content range described in claims and is not conducive to the conversion of intermediate species produced during the reaction. By comparing embodiment 5 with embodiment 6, selectivities of light olefins in the two embodiments exceed 50% and methane selectivities are less than 5%. However, the CO conversion in embodiment 5 is higher because the content of the multicomponent metal composite in the entire catalyst in embodiment 5 is in the preferred range, so the CO conversion is higher.

(49) For the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure in embodiments 6 and 7, the crystal size, the size of secondary particles stacked by the crystal particles and mesopore channel size are within the range of the claims. However, relative to embodiment 6, the crystal size, the size of secondary particles and mesopore channel size in embodiment 7 are within the preferred range, so embodiment 7 shows better CO conversion and selectivity. However, reference example 8 is not within the claims, shows that the crystallization degree of inorganic solid acid is not good, and catalytic conversion cannot be better conducted. Therefore, the CO conversion and the selectivity are significantly worse. Thus, the crystal size, the secondary particle size and the mesopore channel size of the inorganic solid acid are extremely important for the control of the catalytic conversion and the product selectivity.

(50) Embodiment 8

(51) A composite catalyst of the multicomponent metal composite and the inorganic solid acid with hierarchical pore structure is prepared by a coating growth method.

(52) The method relates to the growth of a single layer or a part of inorganic solid acid material with hierarchical pore structure on the prepared multicomponent metal composite by a hydrothermal method and the like.

(53) By taking CuZn metal and co-precipitation method as an example, the method is not limited to bimetal and is suitable for other metals, and the relative proportion of different metals can be changed. Ammonia, ammonium carbonate or ammonium bicarbonate can be used as a precipitant.

(54) 4.8 g of copper nitrate trihydrate and 5.95 g of zinc nitrate hexahydrate are weighed and dissolved in 100 ml of deionized water. 11 g of ammonium carbonate is weighed and dissolved in 100 ml of deionized water. The two groups of solutions are simultaneously added dropwise to the deionized water under ultrasonic agitation at constant temperature of 70 C. and precipitated, with an ultrasonic power of 5 W and a stirring rate of 500 rpm. Then, the precipitate is aged at 70 C. for 3 h and washed with 70 C. of deionized water to be neutral. Then, the precipitate is dried at 110 C. for 12 h and calcined at 500 C. for 1 h to prepare CuZn composite oxide, wherein Cu/Zn mole ratio is 1:1. By this method, CuZn oxide of different molar ratios can be obtained.

(55) 10 ml of silica sol solution (containing 30 wt % of SiO.sub.2) is added to 10 ml of deionized water; 1 g of the above multicomponent metal composite is weighed and added to the solution; the mixture is infiltrated by solution at shaking table for 2 h so that the solid and liquid are separated; the solid is placed in an oven of 120 C. and dried for 12 h and calcined at 500 C. for 2 h so that the oxide is covered with a layer of SiO.sub.2 film; and 11.37 g of TPAOH, 9.68 g of ethanol, 0.06 g of aluminium oxide and 50 ml of H.sub.2O are weighed, stirred and dissolved. The above oxide is added, and stirred. 9.65 g of TEOS is weighed and dropwise added to the above solution, and stirred for 6 h. The mixture is crystallized at 180 C. for 72 h, filtered and washed, dried in an oven of 60 C. and calcined at 500 C. for 5 h to obtain the Cu.sub.1Zn.sub.1@SiAl catalyst with a core-shell structure, wherein the oxide accounts for 50 wt % of the total mass of the catalyst. According to the method, the metal components and the proportions thereof as well as the loading capacity of the multicomponent metal composite can be changed.

(56) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 311 m.sup.2/g with micropore size distribution of 3-4 , and the mesoporous specific surface area is 203 m.sup.2/g with mesopore size distribution of 13-30 nm, and the macroporous specific surface area is 171 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains CuO, ZnO and the silicon-aluminum inorganic solid acid with MFI topology, and the crystal size of the metal oxide and the crystal size of the inorganic solid acid are 8-20 nm and 55-70 nm, respectively. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 30-60 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 8-20 nm and the secondary particle size is 20-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 408 C., and the amount of sites of the medium strong acid is 0.7 mol/kg.

(57) Embodiment 9

(58) The preparation process is substantially the same as that of embodiment 8, and the difference is that in the preparation process of the multicomponent metal composite, the predecessors are replaced with zinc nitrate hexahydrate, cobalt nitrate hexahydrate and aluminum nitrate nonahydrate, wherein the mass of zinc nitrate hexahydrate is 5.95 g, and the precursors are weighed according to the element molar ratio of Zn:Co:Al=1:0.01:1 and dissolved in 100 ml of deionized water. 14.3 g of ammonium carbonate is weighed and dissolved in 100 ml of deionized water.

(59) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 297 m.sup.2/g with micropore size distribution of 3-4 , and the mesoporous specific surface area is 122 m.sup.2/g with mesopore size distribution of 2-8 nm, and the macroporous specific surface area is 111 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains Co.sub.3O.sub.4, Co.sub.2O.sub.3, ZnO, Al.sub.2O.sub.3, ZnCo.sub.2O.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, and the crystal size of the metal oxide and the crystal size of the inorganic solid acid are 9-17 nm and 50-60 nm, respectively. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 100-500 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 9-17 nm and the secondary particle size is 20-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 363 C., and the amount of sites of the medium strong acid is 0.6 mol/kg.

(60) In reference example 9, the preparation process is substantially the same as that of embodiment 8, and the difference is that in the preparation process of the multicomponent metal composite, ultransonic treatment is not used, aging is conducted at 90 C. for 0.5 h and the crystallization temperature is changed to 300 C., causing that the final catalyst cannot form a good crystal form and the finally obtained crystal size is less than 1 nm. The crystallization time is controlled as 1.5 h in the process of coating the inorganic solid acid. For the final catalyst, the microporous specific surface area is 148 m.sup.2/g with micropore size distribution of 4-6 , and the mesoporous specific surface area is 27 m.sup.2/g with mesopore size distribution of 20-47 nm, and the macroporous specific surface area is 7 m.sup.2/g. The crystal size of the metal oxide is less than 1 nm and the secondary particle size is 10 nm-50 m. The crystal size of the inorganic solid acid is 53-79 nm; the secondary particle size of the inorganic solid acid is 300-600 m; NH.sub.3 desorption peak temperature corresponding to medium strong acid is 410 C.; and the amount of sites of the medium strong acid is 0.05 mol/kg.

(61) In reference example 10, the preparation process is substantially the same as that of embodiment 8, and the difference is that in the synthesis process of the multicomponent metal composite, the power of ultrasonic treatment is 0.5 W, aging is conducted at 30 C. for 3 days and the crystallization temperature is changed to 800 C., so that the crystal size of the final catalyst is greater than 30 nm. For the final catalyst, the microporous specific surface area is 757 m.sup.2/g with micropore size distribution of 4-6 , and the mesoporous specific surface area is 147 m.sup.2/g with mesopore size distribution of 8-14 nm, and the macroporous specific surface area is 150 m.sup.2/g. The crystal size of the metal oxide is 30 nm-70 nm and the secondary particle size is 100 nm-50 m. The crystal size of the inorganic solid acid is 80-120 nm and the secondary particle size of the inorganic solid acid is 200-800 m. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 430 C., and the amount of sites of the medium strong acid is 4 mol/kg.

(62) In embodiment 8, reference example 9 and reference example 10, under reaction conditions of 370 C., 2 MPa and volume space velocity of 7000 h.sup.1, reaction results are shown in the table below.

(63) In embodiment 9, under reaction conditions of 400 C., 2.5 MPa and volume space velocity of 4000 h.sup.1, reaction results are shown in the table below.

(64) TABLE-US-00005 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 8 14.27 53.86 1.09 90.77 50.16 8.14 Embodiment 9 17.40 57.00 8.4 76.68 63.97 16.89 Reference Example 9 23.44 50.68 34.79 58.24 17.35 6.97 Reference Example 1.78 66.18 8.31 90.07 27.10 1.62

(65) The crystal sizes of the multicomponent metal composite in the reference example 9 are very small, wherein many metals are present in the form of clusters of atoms formed by single atom or a few atoms, and the particle size is less than the preferred range described in the claims and also less than the crystal size range described in the claims. Although the CO conversion of the reference example 9 is increased, the methane selectivity is increased significantly by more than 30%, while the selectivity of the light olefins is decreased to be less than 20%. In the reference example 10, the crystal size of the multicomponent metal composite is larger than the upper limit of the crystal size range described in the claims. The excessively large particle size and the reduced specific surface area cause the insufficient capacity to activate and convert the synthesis gas, resulting in very low CO conversion. Meanwhile, the hydrogenation is more serious, so the selectivity of the light olefins has declined. Therefore, the crystal size of the metal composite is critical to control of the catalytic performance.

(66) Embodiment 10

(67) The preparation process and method are substantially the same as those of embodiment 5, and the difference is that in the preparation process of the multicomponent metal composite, 17.33 g of zinc nitrate hexahydrate, 0.17 g of cobalt nitrate hexahydrate and 22.1 g of titanium chloride are respectively weighed and dissolved in 300 ml of deionized water; and 60.5 g of ammonium carbonate is weighed and dissolved in 300 ml of deionized water. The two groups of solutions are simultaneously added dropwise to the deionized water under ultrasonic agitation at constant temperature of 70 C. and precipitated, with an ultrasonic power of 5 W and a stirring rate of 500 rpm. Then, the precipitate is aged at 70 C. for 3 h and washed with 70 C. of deionized water to be neutral. Then, the precipitate is dried at 110 C. for 12 h and calcined at 500 C. for 1 h to prepare ZnCo.sub.0.05Ti.sub.2 composite oxide, wherein Co/Ti/Zn mole ratio is 0.05/2/1.

(68) By this method, ZnCoTi oxide of different molar ratios can be obtained.

(69) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 251 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 213 m.sup.2/g with mesopore size distribution of 4-13 nm, and the macroporous specific surface area is 216 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains ZnO, Co.sub.3O.sub.4, TiO.sub.2, ZnCo.sub.2O.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 8-20 nm and the crystal size of the inorganic solid acid is 60-80 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 300-700 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 8-20 nm and the secondary particle size is 30-120 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 377 C., and the amount of sites of the medium strong acid is 2 mol/kg.

(70) In reference example 11, the preparation process is substantially the same as that of embodiment 10, and the difference is that the ratio of the metal elements in the multicomponent metal composite is changed to Zn.sub.0.05Co.sub.3Ti.sub.2 to prepare the metal precursor solution according to the proportion for synthesis when the metal precursors are weighed. XRD shows that the multicomponent metal composite contains ZnO, CoO, Co, ZnCo.sub.2O.sub.4 and CoTiO.sub.3. The metal Co content is 30% in all metal atoms according to the atomic number, exceeding 10% of the claims. The crystal size of the multicomponent metal composite is 8-40 nm and the secondary particle size is 30-120 nm.

(71) Under reaction conditions of 400 C., 2 MPa and volume space velocity of 6000 h.sup.1, reaction results are shown in the table below.

(72) TABLE-US-00006 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 10 7.83 59.64 2.99 89.17 57.40 7.84 Reference Example 35.78 78.01 27.76 21.67 17.18 50.57

(73) For reference example 11, the C.sub.5+ product of the reaction product accounts for more than 50% and methane accounts for more than 20% under the same conditions. Since the content of the metallic state Co in the catalyst is too high to be within the scope of the claims, the reaction tends to occur under the conventional Fischer-Tropsch synthesis path and the product is limited by the ASF distribution, resulting in low selectivity of light olefins and generating more long-carbon-chain hydrocarbons.

(74) Embodiment 11

(75) The preparation process and method are substantially the same as those of embodiment 8, and the difference is that the prepared silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is mixed with 10% of ammonium nitrate solution with a mass ratio of 1:500 and stirred at 80 C. for 8 h. After sucked and filtered and dried at room temperature, the resulting solid is mixed with 1% of copper nitrate solution with a mass ratio of 1:500 and stirred at 80 C. for 8 h. After sucked and filtered and dried at room temperature, the resulted mixture is dried in an oven at 110 C. for 14 h and calcined in air at 500 C. for 1 h to obtain Cu-ion exchanged multicomponent metal composite.

(76) The preparation process of the multicomponent metal composite is different in that the preparation process of metal precursors includes weighing 5.95 g of zinc nitrate hexahydrate, weighing ammonium molybdate according to an element mole ratio of 1:1 and dissolving in 100 ml of deionized water. 11 g of ammonium carbonate is weighed and dissolved in 100 ml of deionized water.

(77) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 239 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 271 m.sup.2/g with mesopore size distribution of 4-13 nm, and the macroporous specific surface area is 198 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains ZnO, CuO, MoO.sub.3, ZnMoO.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 12-26 nm and the crystal size of the inorganic solid acid is 60-90 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 300-700 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 12-26 nm and the secondary particle size is 30-120 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 345 C., and the amount of sites of the medium strong acid is 0.5 mol/kg.

(78) Embodiment 12

(79) The preparation process is substantially the same as that of embodiment 11, and the difference is that metal elements in the multicomponent metal composite are replaced to ensure that the amount of replacing metal atoms is equal to the amount of replaced metal atoms. Ammonium molybdate is replaced with VO.sub.2NO.sub.3 when the metal precursor solution is prepared.

(80) Embodiment 13

(81) The preparation process is substantially the same as that of embodiment 11, and the difference is that metal elements in the multicomponent metal composite are replaced to ensure that the amount of replacing metal atoms is equal to the amount of replaced metal atoms. Ammonium molybdate is replaced with manganous nitrate when the metal precursor solution is prepared.

(82) Under reaction conditions of 360 C., 0.8 MPa and volume space velocity of 3000 h.sup.1, reaction results are shown in the table below.

(83) TABLE-US-00007 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 11 6.84 59.01 4.38 91.85 50.11 3.77 Embodiment 12 6.72 60.16 4.39 83.58 53.07 12.03 Embodiment 13 6.15 58.73 3.79 88.37 63.18 7.84

(84) The difference of embodiments 11, 12 and 13 is that the metal element composition in the multicomponent metal composite is replaced from Mo to V and Mn. The selectivity of the light olefins is gradually increased. This is consistent with the preferred metal elements described in the claims.

(85) Embodiment 14

(86) The preparation process and method are substantially the same as those of embodiment 3, and the difference is that the preparation process and method of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure are as follows: sodium silicate, boehmite, ethylenediamine and water are weighed according to the mass ratio of SiO.sub.2:Al.sub.2O.sub.3:R:H.sub.2O=300:15:30:100; after the materials are stirred in 250 ml of beaker at 50 C. and aged for 1 h, the materials are stirred at 30 C. for secondary aging; after stirred at 500 rpm for 72 h, the mixture is transferred to a hydrothermal reactor and crystallized in an oven at 150 C. for 47 h; the water bath is quenched to room temperature; centrifugal washing is repeated so that the pH of the supernatant is 7 at the end of washing; and after dried at 110 C. for 17 h, the precipitate is calcined in air at 550 C. for 3 h to obtain the silicon-aluminum inorganic solid acid with hierarchical pore structure.

(87) The preparation process of the metal precursors of the multicomponent metal composite includes weighing 5.95 g of zinc nitrate hexahydrate, weighing palladium nitrate and zirconium nitrate pentahydrate according to an element mole ratio of Zn:Pd:Zr=1:0.01:1 and dissolving in 100 ml of deionized water. 11.3 g of ammonium carbonate is weighed and dissolved in 100 ml of deionized water.

(88) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 239 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 308 m2/g with mesopore size distribution of 4-13 nm, and the macroporous specific surface area is 161 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains ZnO, PdO, ZrO.sub.2, ZnZr.sub.2O.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 12-22 nm and the crystal size of the inorganic solid acid is 60-90 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 300-700 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 12-22 nm and the secondary particle size is 40-120 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 370 C., and the amount of sites of the medium strong acid is 1.6 mol/kg.

(89) Embodiment 15

(90) The preparation process is substantially the same as that of embodiment 14, and the difference is that the atomic ratio of the metal element Zn to the other elements is changed to 5:1 in the preparation process of the metal precursor of the multicomponent metal composite when the metal precursor solution is prepared.

(91) In reference example 12, the preparation process is substantially the same as that of embodiment 14, and the difference is that the atomic ratio of the metal element Zn to the other elements is changed to 0.05:1 in the preparation process of the metal precursor of the multicomponent metal composite when the metal precursor solution is prepared.

(92) Under reaction conditions of 380 C., 1.5 MPa and volume space velocity of 8000 h.sup.1, reaction results are shown in the table below.

(93) TABLE-US-00008 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 14 8.19 54.45 4.07 66.18 55.85 29.75 Embodiment 15 4.73 53.91 4.37 61.28 50.17 34.35 Reference Example 2.58 60.33 5.76 67.34 47.99 26.9

(94) Compared with embodiment 14, reference example 12 changes the ratio of Zn to other elements; and the ratio in the reference 12 is not within the ratio range of claims. Therefore, the CO conversion is very low. Although the ratio in embodiment 15 is within the range of claims but not within the preferred range, the CO conversion is also low.

(95) Embodiment 16

(96) The preparation process and method of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure are substantially the same as those of the embodiment 3, and the difference is that the obtained silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is placed in an ampoule of 102 Pa or more vacuum with constant temperature. The silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is heated at 5 C./min to a temperature of 420 C., then kept for 12 h. Then, the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is sealed and transferred to the glove box with Ar atmosphere, then mixed with molybdenum chloride in accordance with the mass ratio of 1:0.1 and placed on both sides of the quartz ampoule. After put into 102 Pa vacuum, the quartz ampoule is enclosed so that the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure and the molybdenum chloride are enclosed together in the vacuum quartz ampoule. The quartz ampoule filled with the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure and the molybdenum chloride is placed in a tube furnace and heated at 10 C./min to 400 C., and held at 400 C. for 24 hours. Then, the quartz ampoule is dropped to room temperature and broken to obtain MoSiAlP with molybdenum oxide load of 1%.

(97) The preparation process of the multicomponent metal composite is substantially the same as that of embodiment 5. The preparation process of the multicomponent metal composite is different in that the preparation process of metal precursors includes weighing 5.95 g of zinc nitrate hexahydrate, weighing ammonium molybdate according to an element mole ratio of 1:1 and dissolving in 100 ml of deionized water.

(98) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 533 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 133 m.sup.2/g with mesopore size distribution of 3-8 nm, and the macroporous specific surface area is 118 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains MoO.sub.2, ZnO, Al.sub.2O.sub.3, ZnAl.sub.2O.sub.4 and the silicon-aluminum inorganic solid acid with CHA topology, and the crystal size of the metal oxide and the crystal size of the inorganic solid acid are 7-12 nm and 50-60 nm, respectively. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 100-500 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 7-12 nm and the secondary particle size is 20-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 344 C., and the amount of sites of the medium strong acid is 2 mol/kg.

(99) In reference example 13, the preparation process is substantially the same as that of embodiment 16, and the difference is that metal elements in the multicomponent metal composite are replaced to ensure that the amount of replacing metal atoms is equal to the amount of replaced metal atoms. Zinc nitrate is replaced with cerium nitrate when the metal precursor solution is prepared.

(100) In reference example 14, the preparation process is substantially the same as that of embodiment 16, and the difference is that metal elements in the multicomponent metal composite are replaced to ensure that the amount of replacing metal atoms is equal to the amount of replaced metal atoms. Zinc nitrate is replaced with nanometer-sized titania sol when the metal precursor solution is prepared.

(101) Under reaction conditions of 400 C., 3 MPa and volume space velocity of 4000 h.sup.1, reaction results are shown in the table below.

(102) TABLE-US-00009 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 16 8.79 55.87 6.71 84.09 57.50 9.2 Reference Example <1 Reference Example <1

(103) Reference examples 13 and 14 do not contain necessary elements of claims, so have hardly any catalytic activity.

(104) Embodiment 17

(105) The preparation process and method of the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure are the same as those of embodiment 5. The difference is that the preparation process of metal precursors includes weighing 1.73 g of zinc nitrate hexahydrate, weighing 1.49 g of gallium nitrate according to an element mole ratio of Zn:Ga=1:1 and dissolving in 100 ml of deionized water; and weighing according to an element mole ratio of Zn:Ti=1:1 and adding 4.65 g of TiO.sub.2.

(106) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 289 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 267 m.sup.2/g with mesopore size distribution of 5-13 nm, and the macroporous specific surface area is 161 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains ZnO, Ga.sub.2O.sub.3, TiO.sub.2 and the silicon-aluminum inorganic solid acid with CHA topology, and the crystal size of the metal oxide and the crystal size of the inorganic solid acid are 13-20 nm and 60-80 nm, respectively. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 300-700 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 13-20 nm and the secondary particle size is 30-120 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 336 C., and the amount of sites of the medium strong acid is 0.47 mol/kg.

(107) Embodiment 18

(108) The preparation process and method are substantially the same as those of embodiment 3, and the difference is that the preparation of the silicon-phosphorus-aluminum inorganic solid acid with the hierarchical pore structure is as follows: 1.66 g of zinc nitrate hexahydrate, and corresponding amount of cobalt nitrate hexahydrate, 0.5 wt % of aqueous solution of manganese nitrate and titanium chloride according to the molar ratio of element: Zn:Co:Mn:Ti=1:0.05:1:1 are weighed to prepare a mixed solution A; and 15.41 g of ammonium carbonate is weighed and dissolved in 100 ml of water to prepare a solution B.

(109) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The microporous specific surface area is 316 m.sup.2/g with micropore size distribution of 4-5 , and the mesoporous specific surface area is 140 m.sup.2/g with mesopore size distribution of 3-9 nm, and the macroporous specific surface area is 99 m.sup.2/g. X-ray diffraction (XRD) shows that the multicomponent metal composite contains Co.sub.2O.sub.3, Co.sub.3O.sub.4, MnO.sub.2, TiO.sub.2, ZnCo.sub.2O.sub.4, ZnMnO.sub.3 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 9-18 nm and the crystal size of the inorganic solid acid is 50-60 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid is 100-500 m. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 9-18 nm and the secondary particle size is 20-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 368 C., and the amount of sites of the medium strong acid is 2.3 mol/kg.

(110) In embodiments 17 and 18, under reaction conditions of the catalyst: 400 C., 3.5 MPa and volume space velocity of 4000 h.sup.1, reaction results of embodiments 17 and 18 are shown in the table below.

(111) TABLE-US-00010 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 17 7.42 58.19 2.59 89.99 57.18 7.42 Embodiment 18 12.83 57.64 5.33 92.77 67.90 1.90

(112) In embodiment 19, under reaction conditions of the catalyst in embodiment 17: 400 C., 3.5 MPa and volume space velocity of 1500 h.sup.1, results as reaction results of embodiment 19 are shown in the table below.

(113) In embodiment 20, under reaction conditions of the catalyst in embodiment 18: 400 C., 3.5 MPa and volume space velocity of 1500 h.sup.1, results as reaction results of embodiment 20 are shown in the table below.

(114) TABLE-US-00011 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 19 18.74 55.31 3.02 85.90 50.24 11.08 Embodiment 20 30.18 58.44 5.96 89.67 63.70 4.37

(115) In reference example 15, under reaction conditions of the catalyst in embodiment 17: 400 C., 3.5 MPa and volume space velocity of 300 h.sup.1, results as reaction results of reference example 15 are shown in the table below.

(116) In reference example 16, under reaction conditions of the catalyst in embodiment 18: 400 C., 3.5 MPa and volume space velocity of 300 h.sup.1, results as reaction results of reference example 16 are shown in the table below.

(117) TABLE-US-00012 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Reference 49.33 67.17 12.88 78.53 24.76 8.59 Example 15 Reference 63.87 69.44 15.02 75.24 13.87 9.74 Example 16

(118) Embodiments 17-20 and reference examples 15-16 change the reaction space velocity conditions without changing the catalyst. The space velocity of embodiments 17-18 is within the preferred range of the claims, and thus shows the highest selectivity of the light olefins, while the space velocity of embodiments 19-20 is not within the preferred range but is still within the scope of the claims, so the selectivity of light olefins is till high. However, in the reference examples 15-16, since the reaction space velocity is not within the scope of the claims, the selectivity of light olefins is very low.

(119) Embodiment 21

(120) A composite catalyst of the multicomponent metal composite and the silicon-aluminum inorganic solid acid with hierarchical pore structure is prepared by a chemical compounding method.

(121) The multicomponent metal composite of CaMnAl and silicon-aluminum inorganic solid acid with hierarchical pore structure are taken as examples.

(122) The raw materials of 30% silica sol (mass concentration), aluminum sulfate, calcium carbonate, N,N,N-trimethyl-adamantane ammonium hydroxide (R) and deionized water are weighed according to the oxide SiO:Al.sub.2O.sub.3:Ca.sub.2O:R.sub.2O:H.sub.2O=40:1:7:5:900 (mass ratio); after mixing at room temperature and stirring at 60 C. and 200 rpm for 24 h, the mixture is transferred to a hydrothermal reactor and crystallized at 155 C. for 6 d. The mixture is naturally cooled to room temperature and transferred to a beaker to have a water bath at 70 C. Ammonium chloride is added according to a ratio of 100 ml of stock solution to 4 g of ammonium chloride, stirred at constant temperature for 3 h and subjected to centrifugal washing repeatedly so that the pH of the supernatant is 7 at the end of washing. After the precipitate is dried at 120 C. for 24 h, the precipitate is calcined in air at 650 C. for 3 h to obtain the silicon-aluminum inorganic solid acid with hierarchical pore structure.

(123) The prepared silicon-aluminum inorganic solid acid with hierarchical pore structure is weighed; 1.49 g of manganese nitrate tetrahydrate is weighed; anhydrous calcium nitrate and aluminum nitrate nonahydrate are weighed according to an element mole ratio of Mn:Ca:Al=1:0.1:1 and dissolved into 100 ml of aqueous solution; CuZnAl is introduced into the silicon-aluminum inorganic solid acid with hierarchical pore structure through an immersion method, CaMnAl is introduced into the silicon-aluminum inorganic solid acid with hierarchical pore structure, dried in vacuum at room temperature and calcined in still air at 520 C. for 1.5 h to obtain Ca.sub.0.1Mn.sub.1Al.sub.1/mesoSiAl. The loading capacity of the multicomponent metal composite is 50 wt %. According to the method, the metal components and the proportions thereof as well as the loading capacity of the multicomponent metal composite can be changed.

(124) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. The total specific surface area is 565 m.sup.2/g, wherein the microporous specific surface area accounts for 27% of the total specific surface area and the micropore size distribution is 3-4 ; the mesoporous specific surface area accounts for 57% of the total specific surface area and the mesopore size distribution is 6-12 nm; and the macroporous specific surface area accounts for 16% of the total specific surface area. X-ray diffraction (XRD) shows that the multicomponent metal composite contains CaO, MnO.sub.2, Al.sub.2O.sub.3 and the silicon-aluminum inorganic solid acid with CHA topology, the crystal size of the metal oxide is 5-13 nm and the crystal size of the inorganic solid acid is 40-70 nm. Scanning electron microscopy (SEM) shows that the secondary particle size of the silicon-aluminum inorganic solid acid with hierarchical pore structure is 10-100 m and the crystal size of the inorganic solid acid is 10-100 nm. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 5-13 nm and the secondary particle size is 15-50 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 370 C., and the amount of sites of the medium strong acid is 6 mol/kg.

(125) Embodiment 22

(126) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring time is controlled to 18 h, the mixture is transferred to a hydrothermal reactor and crystallized at 170 C. for 5 d.

(127) For the obtained catalyst with hierarchical pore structure, the total specific surface area is 493 m.sup.2/g, wherein the microporous specific surface area accounts for 24% of the total specific surface area and the micropore size distribution is 3-4 ; the mesoporous specific surface area accounts for 53% of the total specific surface area and the mesopore size distribution is 5-11 nm; and the macroporous specific surface area accounts for 23% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 392 C., and the amount of sites of the medium strong acid is 3.1 mol/kg.

(128) Embodiment 23

(129) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring time is controlled to 3 h, the mixture is transferred to a hydrothermal reactor and crystallized at 165 C. for 5 d+10 h. Finally, the mixture is calcined at 620 C. for 80 min.

(130) For the obtained catalyst with hierarchical pore structure, the total specific surface area is 408 m.sup.2/g, wherein the microporous specific surface area accounts for 16% of the total specific surface area and the micropore size distribution is 3-4 ; the mesoporous specific surface area accounts for 53% of the total specific surface area and the mesopore size distribution is 5-13 nm; and the macroporous specific surface area accounts for 31% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 389 C., and the amount of sites of the medium strong acid is 3.4 mol/kg.

(131) Reference Example 17

(132) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring temperature is controlled to 90 C. and stirring time is controlled to 1 h, the mixture is transferred to a hydrothermal reactor and crystallized at 215 C. for 7 d. Finally, the mixture is calcined at 550 C. for 4 h.

(133) For the obtained catalyst with hierarchical pore structure, the total specific surface area is 390 m.sup.2/g, wherein the microporous specific surface area accounts for 66% of the total specific surface area and the micropore size distribution is 3-4 ; the mesoporous specific surface area accounts for 26% of the total specific surface area and the mesopore size distribution is 2-4 nm; and the macroporous specific surface area accounts for 8% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 403 C., and the amount of sites of the medium strong acid is 4.1 mol/kg.

(134) Reference Example 18

(135) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring temperature is controlled to 30 C. and the stirring time is controlled to 48 h, the mixture is transferred to a hydrothermal reactor and crystallized at 175 C. for 8 d. Finally, the mixture is calcined at 550 C. for 3 h.

(136) For the obtained catalyst with hierarchical pore structure, the total specific surface area is 314 m.sup.2/g, wherein the microporous specific surface area accounts for 81% of the total specific surface area and the micropore size distribution is 3-4 ; the mesoporous specific surface area accounts for 14% of the total specific surface area and the mesopore size distribution is 2-4 nm; and the macroporous specific surface area accounts for 5% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 368 C., and the amount of sites of the medium strong acid is 0.9 mol/kg.

(137) Under reaction conditions of 375 C., 3.7 MPa and volume space velocity of 6000 h.sup.1, reaction results are shown in the table below.

(138) TABLE-US-00013 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 21 37.15 54.01 4.38 89.63 65.12 5.99 Embodiment 22 33.68 58.39 2.75 89.99 70.50 7.26 Embodiment 23 28.97 53.66 3.21 91.57 73.58 5.22 Reference Example 30.01 57.18 8.37 79.44 49.36 12.19 Reference Example 25.62 60.14 14.29 73.19 36.04 12.52

(139) Compared with reference examples 17-18, embodiments 21-23 show better selectivity of light olefins because the content distribution of the three-level pore channels in reference examples 17-18 is not within the preferred range. However, embodiments 22 and 23 have a higher selectivity of light olefins than embodiment 21 because the macroporous content of embodiment 21 is not within the preferred range and the contents of the three-level pore channels of embodiments 22-23 are not only within the preferred range but also in the more preferred range, so embodiments 22-23 have excellent performance.

(140) Embodiment 24

(141) A composite catalyst of the multicomponent metal composite and the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is prepared by a chemical compounding method.

(142) The raw materials of white carbon black, aluminum nitrate, phosphoric acid, TEAOH(R) and deionized water are weighed according to the oxide MgO:SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O=2:18:16:32:55:150 (mass ratio); after mixing at room temperature and stirring at 30 C. and 500 rpm for 10 h, the mixture is transferred to a hydrothermal reactor, crystallized at 200 C. for 29 h; and the mixture is continuously stirred at stirring speed of 100 rpm while crystallizing. The water bath is quenched to room temperature. Centrifugal washing is conducted repeatedly so that the pH of the supernatant is 7 at the end of washing. After the precipitate is dried at 110 C. for 24 h, the precipitate is calcined in air at 600 C. for 3 h to obtain the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure.

(143) The silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure is prepared by the above method. 1.54 g of manganese nitrate tetrahydrate is weighed; and calcium chloride and chromic nitrate nonahydrate are weighed according to a mole ratio of Mn:Ca:Cr=2:0.2:1 and dissolved into an aqueous solution to prepare a mixed solution A, wherein the mass ratio of the inorganic solid acid to Cr is 2:1. 6.3 g of ammonium carbonate is weighed and dissolved in 100 ml of water to prepare a solution B; the solution B is dropwise added at 50 C. to the mixed solution A stirred at a power of 7 W with tip ultransonic and a speed of 400 rpm; centrifugal washing is conducted so that the pH of the supernatant is 7 at the end of washing; the mixture is dried in the air at 110 C. and calcined in still air at 500 C. for 1 h to obtain Ca.sub.0.2Mn.sub.2Cr.sub.1/MgSiPAl. Then, through Ca.sub.0.2Mn.sub.2Cr.sub.1/MgSiPAl as a carrier, palladium diacetate Co(Ac).sub.2 is accurately weighed and dissolved in water, and introduced into Ca.sub.0.2Mn.sub.2Cr.sub.1/MgSiPAl by impregnation, wherein the mole ratio of Co to Mn is 0.01. According to the method, the metal components and the proportions thereof as well as the loading capacity of the multicomponent metal composite can be changed.

(144) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is 2-4 ; and mesopore size distribution is 4-8 nm. The total specific surface area is 416 m.sup.2/g, wherein the microporous specific surface area accounts for 57%; the mesoporous specific surface area accounts for 21% of the total specific surface area; and the macroporous specific surface area accounts for 22% of the total specific surface area. The secondary particle size of the silicon-aluminum inorganic solid acid is 100-500 m and the crystal size is 5-70 nm. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 0.5-16 nm and the secondary particle size is 10-100 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 371 C., and the amount of sites of the medium strong acid is 2.1 mol/kg.

(145) Embodiment 25

(146) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring temperature is controlled to 40 C. and the stirring time is controlled to 2 h, the mixture is transferred to a hydrothermal reactor and crystallized at 180 C. for 2 d. Finally, the mixture is calcined in flowing air at 550 C. for 4 h.

(147) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is 2-5 ; and mesopore size distribution is 5-9 nm. The total specific surface area is 357 m.sup.2/g, wherein the microporous specific surface area accounts for 43%; the mesoporous specific surface area accounts for 30% of the total specific surface area; and the macroporous specific surface area accounts for 27% of the total specific surface area. The secondary particle size of the silicon-aluminum inorganic solid acid is 50-150 m and the crystal size is 20-80 nm. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 1-13 nm and the secondary particle size is 10-80 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 358 C., and the amount of sites of the medium strong acid is 1.9 mol/kg.

(148) Embodiment 26

(149) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, after precursors are weighed and mixed at room temperature and the stirring temperature is controlled 50 C. and the stirring time is controlled to 1 h, the mixture is transferred to a hydrothermal reactor and crystallized at 165 C. for 5 d+10 h. Finally, the mixture is calcined in still air at 620 C. for 2 h.

(150) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is 3-5 ; and mesopore size distribution is 4-9 nm. The total specific surface area is 4415 m.sup.2/g, wherein the microporous specific surface area accounts for 33%; the mesoporous specific surface area accounts for 35% of the total specific surface area; and the macroporous specific surface area accounts for 32% of the total specific surface area. The secondary particle size of the silicon-aluminum inorganic solid acid is 50-100 m and the crystal size is 40-90 nm. High resolution transmission electron microscopy (HRTEM) shows that the crystal size of the multicomponent metal composite is 3-6 nm and the secondary particle size is 10-90 nm. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 397 C., and the amount of sites of the medium strong acid is 2.7 mol/kg.

(151) Reference Example 19

(152) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, raw materials are weighed according to oxide MgO:SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O:2:18:16:32:10:150 (mass ratio) and precursors are mixed at room temperature. The crystallization temperature is controlled to 150 C. and the time is controlled to 24 h.

(153) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is 3-5 ; and mesopore size distribution is 4-9 nm. The total specific surface area is 95 m.sup.2/g, wherein the microporous specific surface area accounts for 11%; the mesoporous specific surface area accounts for 55% of the total specific surface area; and the macroporous specific surface area accounts for 34% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 320 C., and the amount of sites of the medium strong acid is 0.02 mol/kg.

(154) Reference Example 20

(155) The preparation process of the catalyst is substantially the same as that of embodiment 21, and the difference is that in the preparation process of the silicon-aluminum inorganic solid acid with hierarchical pore structure, raw materials are weighed according to oxide MgO:SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O:2:18:16:32:80:150 (mass ratio) and precursors are mixed at room temperature. The crystallization temperature is controlled to 180 C. and the time is controlled to 72 h. The calcination temperature is controlled to 550 C. and the time is controlled to 30 min in still air.

(156) The N.sub.2 physical adsorption and desorption show that the catalyst has a hierarchical pore structure. Micropore size distribution is 3-5 ; and mesopore size distribution is 4-9 nm. The total specific surface area is 69 m.sup.2/g, wherein the microporous specific surface area accounts for 14%; the mesoporous specific surface area accounts for 24% of the total specific surface area; and the macroporous specific surface area accounts for 62% of the total specific surface area. NH.sub.3 desorption peak temperature corresponding to medium strong acid is 329 C., and the amount of sites of the medium strong acid is 0.03 mol/kg.

(157) Under reaction conditions of 415 C., 3.0 MPa and volume space velocity of 5000 h.sup.1, reaction results are shown in the table below.

(158) TABLE-US-00014 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 24 27.15 60.04 2.34 92.49 65.34 5.17 Embodiment 25 28.96 57.34 1.69 89.79 70.01 8.52 Embodiment 26 31.48 52.29 3.08 91.06 75.48 5.86 Reference Example 5.04 56.80 17.23 55.98 37.44 26.79 Reference Example 2.67 45.18 23.84 46.10 33.27 30.06

(159) For the crystals of embodiments 24-26, the crystal particles and the secondary particles sizes of the multicomponent metal composite and the silicon-aluminum inorganic solid acid satisfy the scope of the claims, and the specific surface areas thereof satisfy the scope of the claims. Moreover, the content of the three-dimensional three-level pore channels and the content of the three-level pore channels formed as described by claims satisfy the preferred range of the claims, wherein embodiments 25-26 present more excellent performance in a more preferred range. In reference examples 19-20, although the three-dimensional three-level pore channels are formed, the ratio of the organic template agent to the water does not satisfy the scope of the claims, the organic template agent in reference example 19 is too little to form sufficient pore structures and the excess amount of the organic template agent in reference example 20 is too much and the calcination time does not satisfy the time range described in the claims. Therefore, the specific surface areas of reference examples 19-20 are lower than the range of the claims, causing that the CO conversion is very low and the selectivity of light olefins is also much lower than that of the catalyst of the present invention.

(160) Embodiment 27

(161) The preparation process of the catalyst is substantially the same as that of embodiment 5, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, copper nitrate hexahydrate is replaced with sodium bicarbonate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:10; and cobalt nitrate hexahydrate is replaced with ferric ammonium citrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:2.

(162) Embodiment 28

(163) The preparation process of the catalyst is substantially the same as that of embodiment 27, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, sodium bicarbonate is replaced with basic magnesium carbonate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(164) Embodiment 29

(165) The preparation process of the catalyst is substantially the same as that of embodiment 27, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, sodium bicarbonate is replaced with potassium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(166) Embodiment 30

(167) The preparation process of the catalyst is substantially the same as that of embodiment 27, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, sodium bicarbonate is replaced with cesium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(168) Embodiment 31

(169) The preparation process of the catalyst is substantially the same as that of embodiment 27, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, sodium bicarbonate is replaced with lanthanum nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(170) Embodiment 32

(171) The preparation process of the catalyst is substantially the same as that of embodiment 5, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, copper nitrate hexahydrate is replaced with 25 wt. % of manganous nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1; cobalt nitrate hexahydrate is replaced with ferric ammonium citrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:2; and y-Al.sub.2O.sub.3 is replaced with gallium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(172) Embodiment 33

(173) The preparation process of the catalyst is substantially the same as that of embodiment 32, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, gallium nitrate is replaced with germanium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(174) Embodiment 34

(175) The preparation process of the catalyst is substantially the same as that of embodiment 32, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, gallium nitrate is replaced with zirconium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(176) Embodiment 35

(177) The preparation process of the catalyst is substantially the same as that of embodiment 32, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, gallium nitrate is replaced with indium nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(178) Embodiments 36-40

(179) The preparation process of the catalyst is substantially the same as those of embodiments 27-31, and the difference is that metal elements in the multicomponent metal composite are replaced and in the preparation of the metal precursor solution, zinc nitrate is replaced with 25 wt. % of manganous nitrate to ensure a ratio of replacing metal atoms to replaced metal atoms is 1:1.

(180) Under reaction conditions of 400 C., 3.0 MPa and volume space velocity of 6000 h.sup.1, reaction results are shown in the table below.

(181) TABLE-US-00015 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Embodiment 27 15.74 56.23 6.17 86.81 65.93 7.02 Embodiment 28 18.93 52.35 2.63 89.79 73.01 7.58 Embodiment 29 14.28 56.09 9.08 85.13 76.28 5.79 Embodiment 30 13.75 56.77 11.45 85.20 67.44 3.35 Embodiment 31 17.53 60.18 1.68 86.30 73.17 12.02 Embodiment 32 27.90 64.94 2.54 95.47 75.04 1.99 Embodiment 33 28.06 58.14 1.78 90.79 70.01 7.43 Embodiment 34 32.68 57.03 3.58 92.13 74.78 4.29 Embodiment 35 33.67 56.93 6.28 86.98 66.12 6.74 Embodiment 36 16.53 53.17 5.62 88.62 63.74 5.76 Embodiment 37 19.02 52.35 2.63 89.79 73.01 7.58 Embodiment 38 13.53 60.17 9.08 85.13 73.66 5.79 Embodiment 39 16.02 62.37 15.62 75.20 60.03 9.18 Embodiment 40 18.24 53.04 11.78 86.30 69.83 1.92

(182) Reference Example 21

(183) As reference example 21, a mixture obtained by mechanically mixing a commercial Na-ZSM-5 molecular sieve with a composite oxide Co.sub.0.1Cr.sub.3Zn.sub.2 prepared by a coprecipitation method is used as the catalyst. Under the same conditions, the selectivity of light alkane and light olefins is not greater than 20% a great number of methane is generated; and the catalyst has poor stability and will be deactivated after 15 hours. Because the molecular sieve only contains the micropore structure and does not have the mesopore structure, carbon deposition generated in the reaction is very easy to block micropores, causing deactivation.

(184) Reference Example 22

(185) As reference example 22, the commercial CuZnAl catalyst used for methanol synthesis and a commercial MTO catalyst SAPO-34 without a hierarchical pore structure are mechanically mixed according to a mass ratio of 1:1 and reactions are carried out under the same conditions. Only alkanes are obtained, and olefins are hardly generated. Because the commercial SAPO-34 molecular sieve does not have the hierarchical pore structure as in claims, it is not beneficial for the mass transfer, causing excessive hydrogenation in the product and few olefins generated in the products.

(186) Reference Example 23

(187) By taking the carbon nanotube as a carrier and loading FeN nano-particles in a tube channel, the gathering and the growth of the nano-particles can be limited to avoid deactivation. Through promotion of K and Mn, K.sub.0.4Mn.sub.1.0FeN@CNTs is obtained and light olefins can be generated selectively. Under conditions of 300 C., 5 bar, space velocity of 15000 h.sup.1 and H.sub.2/CO/Ar=47.5/47.4/5.1, the CO conversion is 11.9% and the selectivity of C.sub.2.sup.C.sub.4.sup. is 43.6%. On the surface of the catalyst, surface carbon species generated through CO dissociation and CH.sub.x intermediate species generated through the reaction of the dissociated hydrogen atom are further coupled mutually on the surface, thereby generating hydrocarbons of different carbon chain lengths or generating alkanes through hydrogenation. Therefore, many products are generated and conform to ASF distribution.

(188) Under reaction conditions of 400 C., 2 MPa and volume space velocity of 4000 h.sup.1, reaction results of reference examples 21 and 22 are shown in the table below.

(189) Under reaction conditions of 300 C., 0.5 MPa and volume space velocity of 15000 h.sup.1, reaction results of the reference example 23 are shown in the table below.

(190) TABLE-US-00016 CO CH.sub.x CH.sub.4 C.sub.2-C.sub.4 C.sub.2.sup.-C.sub.4.sup. C.sub.5+ conversion Selectivity Selectivity Hydrocarbon Olefins Selectivity Catalyst % % % Selectivity % Selectivity % % Reference Example 4.47 34.10 56.08 28.35 15.41 14.71 Reference Example 30.92 45.12 10.53 80.30 0.05 9.17 Reference Example 11.9 60.0 20.0 50.6 43.6 29.4

(191) The selectivity of C.sub.2-C.sub.4 hydrocarbons of the products of the catalyst in embodiments 1-40 in the total hydrocarbon products can reach 60%-95%. The selectivity of the light olefins in the total hydrocarbon products is as high as 50%-85%. Because the metal composite surface of the catalyst has a low hydrogenation activity and low CC coupling activity, the production of a large amount of methane is avoided and the methane selectivity and the selectivity of C.sub.5+ long-carbon-chain hydrocarbon are very low and are less than 10%. The hierarchical pore structure of the inorganic solid acid avoids catalyst deactivation; the CO conversion after successive reaction for 100 hours is stable; and the product selectivity is stable.

(192) Performance of catalysts in embodiments 1-40 are obviously better than that of traditional modified Fischer-Tropsch catalysts and catalysts obtained by mechanically mixing traditional MTO reaction catalysts and methanol synthesis catalysts. The reason is that: after the surface of the metal composite of the catalyst of the present invention is reduced and activated by hydrogen or carbon monoxide containing atmosphere, oxygen vacancy is formed in the surface structure, i.e., the metal is in a coordinative unsaturated state; CO can be catalyzed and activated efficiently to generate one or more than two species of intermediate species CH.sub.x (wherein x=1, 2 or 3); oxygen species on the surface and CO react to generate CO.sub.2; the very active CH.sub.x species are combined with CO to generate CH.sub.xCO, thereby avoiding generation of a large amount of methane; the selectivity of the methane and the selectivity of C.sub.5+ long-carbon-chain hydrocarbon are very low, totally 5% to 10%. The simultaneously generated intermediate species are weakly adsorbed on the surface and can easily desorb from the surface and diffuse into pore channels of the inorganic solid acid, and can be further catalytically converted to generate light hydrocarbon over the catalytically acidic sites. The inorganic solid acid of the present invention has the hierarchical pore structure, thereby avoiding catalyst deactivation; CO conversion after continuous reaction for 100 hours is stable; and the product selectivity is stable. However, the traditional microporous molecular sieve catalyst does not have the hierarchical pore structure, and is very easy to be blocked by the intermediate species generated through the reaction, causing quick catalyst deactivation and being not beneficial for the mass transfer; direct mixing leads to formation of only alkanes, and olefins are hardly produced. In contrast, the catalyst with Fe as major component still follows the Fischer-Tropsch reaction mechanism, i.e., CO is dissociated and adsorbed on the catalyst surface to generate surface carbon and surface oxygen. The surface oxygen reacts with adsorbed hydrogen to generate water. The surface carbon reacts with the surface hydrogen to generate CH.sub.x. The CH.sub.x is strongly adsorbed on the surface, and goes through surface polymerization reaction on the surfaces to generate longer-carbon-chain. Hydrocarbons with different carbon chain lengths are formed depending on the properties of the catalyst surface and desorb into the gas phase as products.

(193) The catalyst provided by the present invention is a composite material and includes effective components of the multicomponent metal composites and the inorganic solid acid with hierarchical pore structures. The synthesis gas can be catalyzed to convert to C.sub.2-C.sub.4 light hydrocarbons. The single pass CO conversion is 10%-60%. The selectivity of light hydrocarbons in all hydrocarbon products can be up to 60%-95%, wherein the selectivity of light olefins (C.sub.2.sup.-C.sub.4.sup.) is 50%-85%. The method has the characteristics of simple process flow, less operation units and low capital investment, and has important application prospects.