CATALYST AND METHOD FOR DIRECT CONVERSION OF SYNGAS TO LIGHT OLEFINS

Abstract

Direct conversion of syngas to light olefins is carried out in a fixed bed or a moving bed reactor with a composite catalyst A+B. The active ingredient of catalyst A is active metal oxide; and catalyst B is one or more than one of zeolite of CHA and AEI structures or metal modified CHA and/or AEI zeolite. A spacing between geometric centers of the active metal oxide of the catalyst A and the particle of the catalyst B is 5 m-40 mm. A spacing between axes of the particles is preferably 100 m-5 mm, and more preferably 200 m-4 mm. A weight ratio of the active ingredients in the catalyst A and the catalyst B is within a range of 0.1-20 times, and preferably 0.3-5.

Claims

1. A catalyst, characterized in that: the catalyst is a composite catalyst A+B and is formed by compounding catalyst component A and catalyst component B in a mechanical mixing mode; the active ingredient of catalyst component A is active metal oxide; catalyst component B is a zeolite of CHA and/or AEI topology; the active metal oxide is one or more than one of MnO, MnCr.sub.2O.sub.4, MnAl.sub.2O.sub.4, MnZrO.sub.4, ZnO, ZnCr.sub.2O.sub.4, ZnAl.sub.2O.sub.4, CoAl.sub.2O.sub.4 and FeAl.sub.2O.sub.4.

2. The skeleton element composition of the zeolite of CHA and AEI topologies may be one or more than one of SiO, SiAlO, SiAlPO, AlPO, GaPO, GaSiAlO, ZnAlPO, MgAlPO and CoAlPO; a molar ratio of (Si+Zn+Mg+Co) to (Al+Ga) in the zeolite composition SiO of the CHA topology and in the skeleton element composition outside is less than 0.6, preferably 0.001-0.48; and a molar ratio of (Si+Zn+Mg+Co) to (Al+Ga) in the zeolite composition SiO of the AEI topology and in the skeleton element composition outside is less than 0.6, preferably 0.001-0.48.

3. The catalyst according to claim 1, wherein the zeolite has the characteristic of medium-strength acid, and the amount of medium-strength acid sites is 0-0.3 mol/kg, preferably 0.003-0.2 mol/kg, and more preferably 0.003-0.06 mol/kg, wherein the peak temperature range corresponding to the desorption peak of NH.sub.3-TPD for medium-strength acid is 275-500 C.; and by using acetone as the probe molecule, the chemical shift of .sup.13C-NMR is in the range of 210-220 ppm.

4. The catalyst according to claim 1, wherein Component A is preferably one or more than one of MnO, MnCr.sub.2O.sub.4, MnAl.sub.2O.sub.4, MnZrO.sub.4, ZnAl.sub.2O.sub.4, CoAl.sub.2O.sub.4 and FeAl.sub.2O.sub.4.

5. The catalyst according to claim 1, wherein a spacing between geometric centers of the active metal oxide of the catalyst component A and the particle of the catalyst component B is 5 m-40 mm; when the Component A is selected from MnO, MnCr.sub.2O.sub.4, MnAl.sub.2O.sub.4 and MnZrO.sub.4, the spacing between particles of the Component A and the Component B is preferably 100 m-5 mm and more preferably 200 m-4 mm; when the component is selected from ZnAl.sub.2O.sub.4, CoAl.sub.2O.sub.4 and FeAl.sub.2O.sub.4, the spacing between particles of the Component A and the Component B is preferably 200 m-3 mm; and when the component is selected from ZnCr.sub.2O.sub.4, the spacing between particles of the Component A and the Component B is preferably 500 m-3 mm.

6. The catalyst according to claim 1, wherein a weight ratio between the active ingredient in the catalyst component A and the catalyst component B is within the range of 0.1-20 times, and preferably 0.3-5.

7. The catalyst according to claim 1, wherein the active metal oxide is composed of grains with a size of 5-30 nm, and a large amount of oxygen vacancies exist within a distance range of 0.3 nm from the surfaces of the grains to the internal direction of the grains, wherein the molar weight of oxygen atoms occupies a value less than 80% of the oxygen molar content in theoretical stoichiometric ratio, preferably, 80%-10%, more preferably 60%-10% and most preferably 50%-10%; the surface oxygen vacancies are defined as: 100%-percent of the molar weight of oxygen atoms in theoretical stoichiometric ratio of oxygen molar weight; and corresponding oxygen vacancy concentration is preferably 20%-90%, more preferably 40%-90% and most preferably 50%-90%.

8. The catalyst according to claim 1, wherein a dispersing agent is also added to the catalyst A; the dispersing agent is one or more than one of Al.sub.2O.sub.3, SiO.sub.2, Cr.sub.2O.sub.3, ZrO.sub.2 and TiO.sub.2; the active metal oxide is dispersed in the dispersing agent; and the content of the dispersing agent in the catalyst A is 0.05-90 wt %, and the balance is the active metal oxide.

9. The catalyst according to claim 1, wherein H may be connected or not connected to O element of the zeolite skeleton; the H may be entirely or partially replaced by one or more than one of Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga, Sn, Fe, Co, Mo and Mn by ion exchange; and the total molar ratio of the substitute metal to oxygen is 0.0002-0.001.

10. A method for preparing light olefins using direct conversion of syngas, wherein syngas is used as reaction raw material; a conversion reaction is conducted on a fixed bed or a moving bed; and the adopted catalyst is the catalyst of claim 1; and the pressure of the syngas is 0.5-10 MPa; reaction temperature is 300-600 C.; space velocity is 300-10000 h.sup.1; and the molar ratio of syngas H.sub.2/CO for reaction is 0.2-3.5, and preferably 0.3-2.5.

11. The catalyst according to claim 2, wherein the zeolite has the characteristic of medium-strength acid, and the amount of medium-strength acid sites is 0-0.3 mol/kg, preferably 0.003-0.2 mol/kg, and more preferably 0.003-0.06 mol/kg, wherein the peak temperature range corresponding to the desorption peak of NH.sub.3-TPD for medium-strength acid is 275-500 C.; and by using acetone as the probe molecule, the chemical shift of .sup.13C-NMR is in the range of 210-220 ppm.

12. The catalyst according to claim 6, wherein H may be connected or not connected to O element of the zeolite skeleton; the H may be entirely or partially replaced by one or more than one of Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga, Sn, Fe, Co, Mo and Mn by ion exchange; and the total molar ratio of the substitute metal to oxygen is 0.0002-0.001.

Description

DETAILED DESCRIPTION

[0029] The present invention is further illustrated below by 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.

Embodiment 1

[0030] I. Preparation of Catalyst A

[0031] (I) Synthesizing ZnO Material with Polar Surface Through an Etching Method:

[0032] (1) weighing 0.446 g (1.5 mmol) of Zn(NO.sub.3).sub.2.6H.sub.2O; weighing 0.480 g (12 mmol) of NaOH and adding to the above container; weighing 30 ml of deionized water and adding to the container; stirring for a time greater than 0.5 h to uniformly mix a solution; increasing the temperature to 160 C. with the reaction time of 20 h; decomposing precipitate into zinc oxide; naturally cooling to room temperature; centrifugally separating reaction liquid to collect the centrifugally separated precipitate; and washing with deionized water twice to obtain ZnO oxide;

[0033] (2) ultrasonically mixing an etching agent with ZnO oxide uniformly under normal temperature; immersing the ZnO oxide in the solution of the etching agent; and generating a complexing or direct reduction reaction by the etching agent and the zinc oxide; and

[0034] heating the above suspended matter; then taking out the suspended matter for washing and filtering the suspended matter to obtain active nano ZnO material having a large amount of surface oxygen holes.

[0035] In Table 1: the mass ratio of the catalyst to the etching agent is 1:3. The mass ratio of the oleic acid to the hexamethylenetetramine is 1:1, without solvent. The mass ratio of the oleic acid to the hydrazine hydrate is 95:5, without solvent. Specific treatment conditions include temperature, treatment time and atmosphere types as shown in Table 1 below.

[0036] (3) Drying or Drying and Reducing:

[0037] after centrifuging or filtering the above obtained products and washing the products with deionized water, drying or drying and reducing the products in an atmosphere which is inert atmosphere gas or a gas mixture of inert atmosphere gas and a reducing atmosphere, wherein the inert atmosphere gas is one or more than one of N.sub.2, He and Ar, the reducing atmosphere is one or both of H.sub.2 and CO, a volume ratio of the inert atmosphere gas to the reducing gas in the drying and reducing gas mixture is 100/10-0/100, the temperature of drying and reducing is 350 C., and time is 4 h. ZnO material with abundant oxygen vacancies on the surface is obtained. Specific samples and preparation conditions thereof are shown in Table 1 below. The oxygen vacancies on the surface are: 100%-percent of the molar weight of oxygen atoms in theoretical stoichiometric ratio of oxygen molar weight.

TABLE-US-00001 TABLE 1 Preparation of ZnO Material and Parameter Performance Drying or Drying and Reducing Surface Sample Temperature/ C. and Temperature/ C. Oxygen Number Etching Agent Carrier Gas (V/V) Time/Minute and Atmosphere Vacancy ZnO 1 oleic 100, N.sub.2 30 30, N.sub.2 21% acid-hexamethylenetetramine ZnO 2 oleic acid 100, 5% H.sub.2/N.sub.2 30 300, 5% H.sub.2/N.sub.2 45% ZnO 3 oleic acid 120, 5% CO/Ar 60 350, 5% CO/Ar 67% ZnO 4 oleic acid-5 wt % hydrazine 140, 5% H.sub.2/Ar 60 310, 5% H.sub.2/Ar 73% hydrate ZnO 5 quadrol 100, 5% NH.sub.3/Ar 30 250, 5% NH.sub.3/Ar 30% ZnO 6 quadrol 140, 5% NO/Ar 90 150, 5% NO/Ar 52% ZnO 7 20 wt % ammonium 100, Ar 30 120, 5% CO/Ar 22% hydroxide ZnO 8 20 wt % ammonium 140, 5% NH.sub.3/5% NO/Ar 90 400, He 29% hydroxide

[0038] The surface oxygen vacancies are the percent of the molar weight of oxygen atoms in theoretical stoichiometric ratio of oxygen molar content within a distance range of 0.3 nm from the surfaces of the grains to the internal direction of the grains. The surface oxygen vacancies are defined as: 100%-percent of the molar weight of oxygen atoms in theoretical stoichiometric ratio of oxygen molar weight.

[0039] As a reference example, ZnO 9 which is not etched in step (2) and has no oxygen vacancy on the surface; and metal Zn 10 by completely reducing Zn. (II) Synthesizing MnO material with polar surface through an etching method: the preparation process is the same as that of the above ZnO. The difference is that, the precursor of Zn is changed for the corresponding precursor of Mn, which is one of manganous nitrate, manganese chloride and manganese acetate (manganous nitrate herein).

[0040] The etching process is the same as step (2) in above (I), and the process of drying or drying and reducing is the same as the preparation processes of products ZnO 3, ZnO 5 and ZnO 8 in step (3) in above (I). The catalyst having a great number of surface oxygen vacancies is synthesized. The surface oxygen vacancies are 67%, 29% and 27%.

[0041] Corresponding products are defined as MnO 1-3.

[0042] (III) Synthesizing Nano ZnCr.sub.2O.sub.4, ZnAl.sub.2O.sub.4, MnCr.sub.2O.sub.4, MnAl.sub.2O.sub.4 and MnZrO.sub.4 Spinel with High Specific Surface Area and High Surface Energy:

[0043] selecting corresponding nitrate, zinc nitrate, aluminum nitrate, chromic nitrate and manganous nitrate as precursors according to chemical composition of the spinel, and mixing the precursors with urea at room temperature in water; aging the above mixed liquid; then taking out the mixed liquid for washing, filtering and drying the obtained precipitants; and calcining the obtained solid under an air atmosphere to obtain spinel oxide which grows along the (110) crystal plane direction. The sample is also treated by the etching method to synthesize the catalyst with a great number of surface oxygen vacancies. The etching process and aftertreatment process are the same as step (2) and step (3) in above (I). The sample has large specific surface area and many surface defects, and can be applied to catalyzing the conversion of syngas.

[0044] Specific samples and preparation conditions thereof are shown in Table 2 below. Similarly, the surface oxygen vacancies are defined as: 100%-percent of the molar weight of oxygen atoms in theoretical stoichiometric ratio of oxygen molar weight.

TABLE-US-00002 TABLE 2 Preparation of Spinel Material and Performance Parameters Stoichiometric Ratio of Metal Elements in Spinel and Molar Etching Agent, Concentration of one Aging Calcining Temperature/ C., Metal in Water Temperature C. Temperature C. Atmosphere and Surface Oxygen Sample Number (mmol/L) and Time h and Time h Time/min Vacancy spinel 1 ZnCr = 1:2, Zn is 50 mM 120, 24 600, 48 oleic acid, 120, 41% 5% H.sub.2/Ar, 60 spinel 2 ZnAl = 1:2, Zn is 50 mM 130, 20 700, 24 oleic acid, 120, 72% 5% H.sub.2/Ar, 60 spinel 3 MnCr = 1:2, Mn is 50 mM 140, 18 750, 16 oleic acid, 120, 83% 5% H.sub.2/Ar, 60 spinel 4 MnAl = 1:2, Mn is 50 mM 145, 16 800, 10 oleic acid, 120, 20% 5% H.sub.2/Ar, 60 spinel 5 MnZr = 1:2, Mn is 50 mM 150, 12 900, 3 oleic acid, 120, 24% 5% H.sub.2/Ar, 60

[0045] (IV) Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 Dispersed Active Metal Oxide

[0046] Preparing Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 dispersed active metal oxide through a precipitate deposition method by taking Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 as carriers. Taking the preparation of dispersed ZnO as an example, commercial Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 carrier is dispersed in a base solution in advance, and then one or more than one of zinc acetate, zinc nitrate, zinc sulfate and other Zn precursors are taken as Zn raw material, mixed with one or more than one of sodium hydroxide, ammonium bicarbonate, ammonium carbonate and sodium bicarbonate, and precipitated at room temperature. Herein, taking zinc nitrate and sodium hydroxide as an example, the molar concentration of Zn.sup.2+ in the reaction liquid is 0.067M; the ratio of molar fractions of Zn.sup.2+ and precipitant may be 1:8; and then aging is conducted at 160 C. for 24 hours to obtain carrier Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 dispersed ZnO oxide, and the contents of the dispersing agents in catalyst A are 0.1 wt %, 10 wt % and 90 wt %.

[0047] The etching process is the same as the preparation processes of products ZnO 3, ZnO 5 and ZnO 8 in step (2) in above (I). The catalyst having a great number of surface oxygen vacancies is synthesized. The surface oxygen vacancies are 65%, 30% and 25%. The aftertreatment process is the same as step (3) in above (I).

[0048] Corresponding products from top to bottom are defined as dispersed oxides 1-3.

[0049] The same method is used to obtain carrier Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 dispersed MnO oxide, wherein the contents of the dispersing agents in catalyst A are 5 wt %, 30 wt % and 60 wt %. The surface oxygen vacancies are 62%, 27% and 28%. Corresponding products from top to bottom are defined as dispersed oxides 4-6.

[0050] II. Preparation of Catalyst B (Zeolite of CHA and AEI Topologies):

[0051] The CHA and/or AEI topology has eight-membered ring orifices and a three-dimensional porous channel and comprises cha cage.

[0052] 1) The Specific Preparation Process is as Follows:

[0053] The raw materials of 30% silica sol (mass concentration), AlOOH, phosphoric acid, TEA (R) and deionized water are weighed according to the oxide SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O=1.6:16:32:55:150 (mass ratio); after mixing at room temperature, auxiliary HF is added with a molar weight of 0.5 time of the template agent; the mixture is stirred and aged at 30 C. for 2 h, and transferred into a hydrothermal reactor and crystallized at 200 C. for 24 h. The autoclave is quenched by water bath to room temperature. Centrifugal washing is conducted repeatedly until the pH of the supernatant is 7 at the end of washing. After the precipitate is dried at 110 C. for 17 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.

[0054] The skeleton element composition of the zeolite of CHA and AEI topologies may be one or more than one of SiO, SiAlO, SiAlPO, AlPO, GaPO, GaSiAlO, ZnAlPO, MgAlPO and CoAlPO.

[0055] O element of part of the skeleton is connected with H, and corresponding products are successively defined as zeolites 1-7.

TABLE-US-00003 TABLE 3 Preparation of Zeolite of CHA or AEI Topology and Performance Parameters Tem- Hydrothermal Deposition Sample Si Aluminum plate Temperature Time Acid Temperature Number Source Source P Source Agent Auxiliary Mass Ratio ( C.) (Day) Amount of NH.sub.3 Zeolite 1 TEOS Sodium Phosphoric TEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 180 1 0.25 349 Meta- Acid 1.6:16:32:55:150 aluminate Zeolite 2 Silica Al(OH).sub.3 Phosphoric Mor HCl SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 150 4 0.27 365 Sol Acid 2.4:19:30:15:150 Zeolite 3 TEOS AlOOH Phosphoric TEAOH HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 160 4 0.13 350 Acid 0.7:15:32:55:150 Zeolite 4 Silica Aluminium Phosphoric DIPEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 170 2.5 0.23 355 Sol Isopropoxide Acid 1.1:17:32:55:150 Zeolite 5 Aluminum Phosphoric TEAOH HF Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 190 1 0.006 331 Sulfate Acid 16:32:55:150 Zeolite 6 Silica Aluminum Phosphoric DIPEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 200 1 0.078 344 Sol Nitrate Acid 0.5:17:32:55:150 Zeolite 7 TEOS Aluminum Phosphoric TEA HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 170 0.7 0.055 347 Sulfate Acid 0.3:18:32:55:150 Zeolite 8 Aluminum Phosphoric TEA HCl Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 160 3.5 0.014 339 Nitrate Acid 11:32:55:150

[0056] 2) The H connected to the O element of skeletons of the above products 1-7 is partly replaced by the following metal ions: Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga. Sn, Fe, Co, Mo and Mn by ion exchange; and the preparation process is:

[0057] SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O=1.1:16:32:55:150 (molar ratio), wherein R is the template agent.

[0058] The aluminum sulphate is mixed with the sodium hydroxide solution, and then silica sol, phosphoric acid, TEA(R) and deionized water are added and stirred for 1 h to obtain initial gel with uniform phase. Then, the mixture is transferred into a synthesis autoclave, is statically crystallized at 165 C. for 80 h, and then is quenched, washed and dried to obtain a zeolite sample. The above samples are then mixed with 0.5 mol/L of metal ion nitrate solution to be exchanged with the solid-liquid mass ratio of 1:30. The mixture is stirred at 80 C. for 6 h, washed and dried. The exchange procedure is conducted twice continuously, and the as-prepared powder is calcined at 550 C. for 3 h to obtain CHA or AEI zeolite after metal ion exchange.

[0059] Corresponding products are successively defined as zeolites 9-22.

TABLE-US-00004 TABLE 4 Preparation of Zeolite of CHA or AEI Topology and Performance Parameters Ratio of Deposition Sample metal ion Exchange Time Acid Temperature of Number Ion and O NH.sub.3-zeolites Aluminum Source Temperature ( C.) (hour) Amount NH.sub.3 zeolite 9 Na 0.04 Zeolite 1 Sodium 80 8 0.23 367 Metaaluminate Zeolite Ca 0.02 Zeolite 2 Al(OH).sub.3 90 7 0.03 364 10 Zeolite K 0.01 Zeolite 3 AlOOH 80 7 0.11 357 11 Zeolite Mg 0.015 Zeolite 4 Aluminium 90 5 0.08 355 12 Isopropoxide Zeolite Ge 0.075 Zeolite 5 Aluminum 80 7 0.15 367 13 Sulfate Zeolite Zr 0.03 Zeolite 6 Aluminum 90 7 0.05 347 14 Sulfate Zeolite Zn 0.005 Zeolite 7 Aluminum 80 8 0.10 370 15 Sulfate Zeolite Cr 0.07 Zeolite 8 Aluminum 70 3 0.25 363 16 Nitrate Zeolite Ga 0.01 Zeolite 1 Aluminum 80 6 0.17 354 17 Nitrate Zeolite Sn 0.001 Zeolite 2 AlOOH 60 5 0.27 357 18 Zeolite Fe 0.0005 Zeolite 3 Aluminum 70 5 0.23 366 19 Nitrate Zeolite Co 0.0003 Zeolite 4 Aluminum 80 6 0.18 367 20 Nitrate Zeolite Mo 0.0005 Zeolite 5 Aluminum 70 3 0.28 369 21 Nitrate Zeolite Mn 0.002 Zeolite 6 AlOOH 70 8 0.29 359 22

TABLE-US-00005 TABLE 5 Preparation of Zeolite Composed of Other Elements and Performance Parameters Sample Template Number Precursor 1 Precursor 2 Precursor 3 Agent Auxiliary Mass Ratio Zeolite TEOS TEA HF SiO.sub.2:R:H.sub.2O = 1.6:55:150 23 Zeolite Silica Sol Al(OH).sub.3 Mor HF SiO.sub.2:Al.sub.2O.sub.3:R:H.sub.2O = 2.4:19:15:150 24 Zeolite Gallium Phosphoric TEAOH HF Ga2O3:H.sub.3PO.sub.4:R:H.sub.2O = 25 Nitrate Acid 15:32:55:150 Zeolite Silica Sol Gallium Phosphoric TEA HF SiO.sub.2:Ga.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 26 Nitrate Acid 1.1:17:32:55:150 Zeolite Zinc Aluminum Phosphoric TEAOH HF ZnO:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 27 Nitrate Sulfate Acid 0.5:16:32:55:150 Zeolite Magnesium Aluminum Phosphoric TEA MgO:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 28 Nitrate Nitrate Acid 0.5:17:32:55:150 Zeolite Cobalt Aluminum Phosphoric TEA HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4:R:H.sub.2O = 29 Nitrate Sulfate Acid 0.4:18:32:55:150 Temperature of Hydrothermal Desorption Peak Sample Temperature Point of Mediate Strong Number ( C.) Time (Day) Acid Amount Acid on NH.sub.3-TPD ( C.) Zeolite 180 1 0.004 344 23 Zeolite 150 4 0.11 357 24 Zeolite 160 4 0.012 347 25 Zeolite 170 2.5 0.07 343 26 Zeolite 190 1 0.0506 360 27 Zeolite 200 1 0.178 357 28 Zeolite 170 0.7 0.255 363 29

[0060] III. Catalyst Preparation

[0061] The catalyst A and the catalyst B in the required ratio are added to the container to achieve the purposes of separation, crushing, uniform mixing and the like, through one or more than one of extrusion force, impact force, shear force and friction force generated by high-speed motion of the material and/or the container, and realize conversion among mechanical energy, thermal energy and chemical energy by regulating the temperature and the atmosphere of carrier gas, thereby further enhancing the interaction between different components.

[0062] In the mechanical mixing process, the mixing temperature can be set as 20-100 C., and the mechanical mixing process can be conducted in an atmosphere or directly in the air. The atmosphere is one or more of: a) nitrogen and/or inert gas; b) mixed gas of hydrogen, nitrogen and/or inert gas, with the volume ratio of hydrogen in the mixed gas being 5-50%; c) mixed gas of carbon monoxide, nitrogen and/or inert gas, with the volume ratio of carbon monoxide in the mixed gas being 5-20%; and d) mixed gas of oxygen, nitrogen and/or inert gas, with the volume ratio of oxygen in the mixed gas being 5-20%. The inert gas is one or more of helium, argon and neon.

[0063] Mechanical stirring: mixing the catalyst A and the catalyst B with a stirring rod in a stirring tank; and regulating the mixing degree and the relative distance of the catalyst A and the catalyst B by controlling stirring time (5 min-120 min) and rate (30-300 r/min).

[0064] Ball milling: Rolling the abrasive and the catalysts at a high speed in a grinding tank thus producing strong impact and milling on the catalysts to achieve the effects of dispersing and mixing the catalyst A and the catalyst B. The ratio of the abrasive (which is stainless steel, agate and quartz; and the size range is 5 mm-15 mm) to the catalysts (the mass ratio scope is 20-100:1) is controlled to regulate the particle size and the relative distance of the catalysts.

[0065] Shaking table mixing: premixing the catalyst A and the catalyst B and placing the catalysts into the container; realizing the mixing of the catalyst A and the catalyst B by controlling the reciprocating oscillation or circumferential oscillation of the shaking table; and realizing uniform mixing and regulating the relative distance by regulating oscillation speed (range: 1-70 r/min) and time (range: 5 min-120 min).

[0066] Mechanical grinding: premixing the catalyst A and the catalyst B and placing the catalysts into a container; and under a certain pressure (range: 5 kgf/cm.sup.2-20 kgf/cm.sup.2), making the ground and the mixed catalysts do relative motion (speed range: 30-300 r/min) to achieve the effects of regulating the particle size and the relative distance of the catalysts and realizing uniform mixing.

[0067] Specific catalyst preparation and parameter features are shown in Table 6.

TABLE-US-00006 TABLE 6 Preparation of Catalysts and Parameter Features Compounding Mode and Condition Mechanical Ball Milling Shaking Grinding Mechanical Abrasive Table Pressure Geometrical Stirring Material, Oscillation (kg) and Center Weight Rate Size Range Speed Relative Distance of A Catalyst Catalyst Catalyst Ratio of A (r/min) and and Catalyst (r/min) and Motion Rate and B Number Component A Component B to B Time (min) Mass Ratio Time (min) (r/min) Particles A ZnO1 Zeolite 1 0.33 5, 30 3 mm B ZnO 2 Zeolite 2 0.5 100, 250 500 m C ZnO3 Zeolite 3 2 5 mm 52 m stainless steel ball, 50:1 D ZnO4 Zeolite 4 1 6 mm 8 m stainless steel ball, 60:1 E ZnO 5 Zeolite 5 1 5, 10 2 mm F ZnO 6 Zeolite 6 3 60, 100 600 m G ZnO 7 Zeolite 7 3 5, 30 300 m H ZnO 8 Zeolite 8 1 100, 300 400 m I spinel 1 Zeolite 9 5 6 mm agate 30 m ball, 100:1 spinel 2 Zeolite 10 1 70, 100 500 m K spinel 3 Zeolite 11 3 15, 200 150 m L spinel 4 Zeolite 12 0.33 20, 300 100 m M spinel 5 Zeolite 13 1 100, 300 400 m N MnO 1 Zeolite 14 3 6 mm 15 m quartz, 100:1 O MnO 2 Zeolite 15 0.33 6 mm 15 m quartz, 100:1 P MnO 3 Zeolite 16 1 10, 100 100 m Q dispersed Zeolite 17 1 100, 250 2 mm oxide 1 R dispersed Zeolite 18 3 5 mm 50 m oxide 2 stainless steel ball, 50:1 S dispersed Zeolite 19 1 10, 100 100 m oxide 3 T dispersed Zeolite 20 4 50, 60 1 mm oxide 4 U dispersed Zeolite 21 3 10, 100 100 m oxide 5 V dispersed Zeolite 22 20 5 mm 5 m oxide 6 stainless steel ball, 100:1 W ZnO1 Zeolite 23 0.5 5, 30 3 mm X ZnO 2 Zeolite 24 1 100, 250 500 m Y ZnO3 Zeolite 25 3 5 mm 52 m stainless steel ball, 50:1 Z ZnO4 Zeolite 26 1.5 6 mm 8 m stainless steel ball, 60:1 Z1 ZnO 5 Zeolite 27 2.5 5, 10 2 mm Z2 ZnO 6 Zeolite 28 1.5 60, 100 600 m Z3 ZnO7 Zeolite 29 2 5, 30 300 m Z4 MnO 1 Zeolite 1 16 100, 200 400 m Z5 ZnO 1 Zeolite 1 0.1 20, 100 500 m Z6 dispersed Zeolite 1 1 20, 300 100 m oxide 1 Z7 spinel 1 Zeolite 1 1.5 60, 100 2 mm Z8 ZnO1 Zeolite 9 4 5 mm 15 m stainless steel ball, 50:1 Z9 MnO 1 Zeolite 2 4.5 50, 120 500 m Z10 dispersed Zeolite 3 2.5 10, 200 200 m oxide 1 Z11 spinel 1 Zeolite 4 3 20, 200 150 m Comparison 1 ZnO 9 Zeolite 1 3 20, 30 2 mm Comparison 2 Zn 10 Zeolite 1 2 60, 100 2 mm

[0068] Example of Catalytic Reactions

[0069] A 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 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).

[0070] 2 g of the above catalyst in the present invention is placed in a fixed bed reactor. The air in the reactor is replaced with Ar; and then the temperature is raised to 300 C. in the H.sub.2 atmosphere, and then the inlet gas is switched to the syngas (H.sub.2/CO molar ratio=0.2-3.5). The pressure of the syngas is 0.5-10 MPa. The temperature is raised to reaction temperature of 300-600 C., and the space velocity of the reaction raw gas is regulated to 500-8000 ml/g/h. On-line chromatography is used to detect and analyze the product.

[0071] The reaction performance can be changed by changing the temperature, pressure, space velocity and H.sub.2/CO molar ratio in the syngas. The sum selectivity of propylene and butylene is 30-75%. The selectivity of light olefins (the sum of ethylene, propylene and butylene) is 50-90%. Due to the low hydrogenation activity of the surface of the metal composite of the catalyst, a large amount of methane will be avoided and the selectivity of methane is low. Table 7 lists specific application and effect data of the catalysts.

TABLE-US-00007 TABLE 7 Specific Application and Effect Data of Catalysts H.sub.2/CO Light Propylene and Temperature Molar Pressure CO olefins CH.sub.4 Butylene Embodiment Catalyst GHSV (h.sup.1) ( C.) Ratio (MPa) Conversion % Selectivity % Selectivity % Selectivity % 1 A 2500 410 2 3.5 13.5 71.8 13.2 47.1 2 B 3000 400 3.5 0.9 27.3 65.5 5.3 43.5 3 C 3000 360 3 2.5 42.5 70.5 14.2 55.3 4 D 8000 370 2 10 38.6 69.6 14.9 45.1 5 E 1000 470 3.5 1.5 20.1 85.8 13.5 71.3 6 F 2000 400 3.5 7 33.3 78.8 6.6 54.3 7 G 3000 380 1.5 2.5 10.3 81.2 11.7 68.6 8 H 500 370 2.5 5 18.6 78.4 9.8 64.3 9 I 2300 370 1 3.5 22.3 61.4 14.2 42.6 10 J 2000 410 2.5 8 33.3 84.7 11.5 71.9 11 K 1000 430 2.5 3 45.7 75.2 9.1 56.3 12 L 2500 520 1 4 15.2 77.2 14.5 57.7 13 M 3000 480 0.5 9 11.5 79.5 13.2 55.1 14 N 3100 470 3 6 40.2 55.5 12.1 44.5 15 O 3200 450 1.5 5 14.3 60.9 13.2 46.3 16 P 3000 450 2.5 5 13.8 75.6 8.9 41.4 17 Q 3000 350 3.5 5 37 72.2 8.6 44.3 18 R 2100 350 2 7 18.6 59.8 10.4 40.2 19 S 2500 400 1 6 19.6 70.8 10.7 45.7 20 T 4000 400 2 4 30.3 76.1 9.4 51.0 21 U 3500 400 3 3 16.4 67.8 11.2 43.4 22 V 3000 450 2.5 4 21.2 70.4 12.3 44.8 23 W 2500 410 2 3.5 11.3 85.3 8.9 71.7 24 X 3000 400 3.5 0.9 15.7 75.3 7.7 60.9 25 Y 3000 360 3 2.5 25.7 60.7 11.7 49.3 26 Z 8000 370 2 10 38.7 76.8 9.7 61.2 27 Z 1 1000 470 1.5 1.5 12.5 85.1 10.8 72.8 28 Z 2 2000 400 3.5 7 26.9 73.3 12.3 60.7 29 Z 3 3000 380 1.5 2.5 11.3 65.7 14.9 49.1 30 Z 4 2000 400 3 3.5 30.2 74.3 8.4 40.9 31 Z5 2500 400 0.3 10 16.8 70.1 5.3 40.0 32 Z6 3000 350 3 4 35.6 75.0 10.3 41.2 33 Z7 4500 400 2.5 3 21.8 65.3 12.2 43.2 34 Z8 4000 400 3 4 28.5 55.8 13.0 42.3 35 Z9 2000 350 2.5 3 38.9 62.3 8.7 48.7 36 Z10 4000 350 3 4 37.1 77.1 13.2 60.5 37 Z11 4200 400 2.5 4 25.8 73.3 10.0 40.7 38 Reference 3000 320 0.5 1 1.9 31.0 31.0 29.2 Example 1 39 Reference 2000 350 1 2 22.7 39.2 46.8 27.1 Example 2 40 Reference 4000 450 3 3 30.5 26.8 22.6 12.9 Example 3 41 Reference 2000 350 2.5 3 0.3 25.5 65.1 19.4 Example 4 42 Reference 2000 410 1.5 3 24.6 46.2 9.7 25.6 Example 5 43 Reference 3000 400 2 3.5 31.2 19.5 10.8 12.7 Example 6 44 Reference 3000 450 2.5 4 8.6 43.6 37.9 28.8 Example 7 45 Reference 3200 350 3 2.7 52.1 43.7 28.1 26.4 Example 8

[0072] In reference example 1, the catalyst component A is ZnO 9, and component B is Zeolite 1.

[0073] In reference example 2, the catalyst component A is Zn 10, and component B is Zeolite 1.

[0074] The component A in the catalyst adopted in reference example 3 is metal ZnCo+Zeolite 1. The molar ratio of Zn to Co is 1:1. The mass ratio of ZnCo to Zeolite 1 is 1:1. Other parameters and the mixing process are the same as those of catalyst A.

[0075] The catalyst adopted in reference example 4 is TiO.sub.2 without surface oxygen vacancy+Zeolite 1. Other parameters and the mixing process are the same as those of catalyst A.

[0076] The zeolite in the catalyst adopted in reference example 5 is a commodity SAPO-34 purchased from Nankai University Catalyst Factory, wherein the temperature of desorption peak of medium-strength acid on NH.sub.3-TPD is 390 C.

[0077] The zeolite in the catalyst adopted in reference example 6 is a commodity ZSM-5 purchased from Nankai University Catalyst Factory, wherein the zeolite is of a full microporous structure and the Si/Al ratio is 30.

[0078] Reaction results of reference examples 5 and 6 show that, the topological structure and acid strength of CHA or AEI are crucial to the modulation of the selectivity of products.

[0079] The distance between the metal oxide and the zeolite in the catalyst adopted in reference example 7 is 10 mm. Other parameters and the mixing process are the same as those of catalyst A.

[0080] The metal oxide in the catalyst adopted in reference example 8 is located in porous channels of the zeolite and is in close contact with the zeolite. Other parameters and the like are the same as those of catalyst A.

[0081] Results of reference examples 7 and 8 show that, the distance between component A and component B is also crucial to product selectivity.

[0082] In the reference technology of the document (Jiao et al., Science 351 (2016) 1065-1068), the acid amount of the adopted SAPO-34 zeolite was large. The amount of the medium-strength acid reached 0.32 mol/kg according to the NH.sub.3-TPD test. Therefore, when the conversion increased to 35%, the selectivity of light olefins was 69%, the selectivity of light paraffins was 20%, o/p decreased to 3.5 and the selectivity of propylene and butylene was 40-50%.

[0083] It is observed from the above table that, the structure of the zeolite including the topologies, acid strength and acid amount of CHA&AEI, and the matching of the distance between the metal oxide and the zeolite are crucial and directly affect the conversion of carbon monoxide and the selectivity of propylene and butylene.