Organic base modified composite catalyst and method for producing ethylene by hydrogenation of carbon monoxide

Abstract

An organic base modified composite catalyst for producing ethylene by hydrogenation of carbon monoxide is a composite catalyst and formed by compounding component I and component II in a mechanical mixing mode. The active ingredient of the component I is a metal oxide; the component II is an organic base modified zeolite of MOR topology; and a weight ratio of the active ingredients in the component I to the component II is 0.1-20, and preferably 0.3-8. The reaction process has an extremely high product yield and selectivity. The selectivity of C.sub.2-C.sub.3 olefins is as high as 78-87%; the selectivity of hydrocarbon products with more than 4 C atoms is less than 10%; the selectivity of a methane side product is extremely low (<9%); and meanwhile, the selectivity of the ethylene is 75-82%.

Claims

1. A catalyst, comprising a component I and a component II, which are compounded in a mechanical mixing mode; wherein, an active ingredient of the component I is a metal oxide; the component II is a zeolite of MOR topology; in the component II, the zeolite of the MOR topology is modified with an amine selected from the group consisting of dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, 1,2-dimethylpropylamine, 1,2-propanediamine, 2-propeneamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutylamine, sec-butylamine, 1,4-butanediamine, tert-butylamine, diisobutylaminehexylamine, 2-ethylhexylamine, hexamethylenediamine, trioctylamine, and combinations thereof; the modification with the amine is to disperse the amine into B acid sites in 12-ring porous channels of the zeolite of the MOR topology.

2. The catalyst according to claim 1, wherein the metal oxide is at least one of MnO.sub.x, Mn.sub.aCr.sub.(1-a)O.sub.x, Mn.sub.aAl.sub.(1-a)O.sub.x, Mn.sub.aZr.sub.(1-a)O.sub.x, Mn.sub.aIn.sub.(1-a)O.sub.x, ZnO.sub.x, Zn.sub.aCr.sub.(1-a)O.sub.x, Zn.sub.aAl.sub.(1-a)O.sub.x, Zn.sub.aGa.sub.(1-a)O.sub.x, Zn.sub.aIn.sub.(1-a)O.sub.x, CeO.sub.x, Co.sub.a Al.sub.(1-a)O.sub.x, Fe.sub.aAl.sub.(1-a)O.sub.x, GaO.sub.x, BiO.sub.x, InO.sub.x, In.sub.aAl.sub.bMn.sub.(1-a-b)O.sub.x, and In.sub.aGa.sub.bMn.sub.(1-a-b)O.sub.x; a specific surface area of MnO.sub.x, ZnO.sub.x, CeO.sub.x, GaO.sub.x, BiO.sub.x and InO.sub.x is 1-100 m.sup.2/g; a specific surface area of Mn.sub.aCr.sub.(1-a)O.sub.x, Mn.sub.aAl.sub.(1-a)O.sub.x, Mn.sub.aZr.sub.(1-a)O.sub.x, Mn.sub.aIn.sub.(1-a)O.sub.x, Zn.sub.aCr.sub.(1-a)O.sub.x, Zn.sub.aAl.sub.(1-a)O.sub.x, Zn.sub.aGa.sub.(1-a)O.sub.x, Zn.sub.aIn.sub.(1-a)O.sub.x, CO.sub.aAl.sub.(1-a)O.sub.x, Fe.sub.aAl.sub.(1-a)O.sub.x, In.sub.aAl.sub.bMn.sub.(1-a-b)O.sub.x, and In.sub.aGa.sub.bMn.sub.(1-a-b)O.sub.x is 5-150 m.sup.2/g; a value range of x is 0.7-3.7, and a value range of a is 0-1; and a value range of a+b is 0-1.

3. The catalyst according to claim 1, wherein a weight ratio of the active ingredient in the component Ito the component II is 0.1-20.

4. The catalyst according to claim 1, wherein a dispersing agent is also added to the component I; the dispersing agent is at least one of Al.sub.2O.sub.3, SiO.sub.2, Cr.sub.2O.sub.3, ZrO.sub.2, TiO.sub.2, Ga.sub.2O.sub.3, activated carbon, graphene, and carbon nanotube; the metal oxide is dispersed in the dispersing agent; and the content of the dispersing agent in the component I is 0.05-90 wt %; and the balance is an active metal oxide.

5. The catalyst according to claim 1, wherein the skeleton element composition of the zeolite of the MOR topology is at least one of Si—Al—O, Ga—Si—O, Ga—Si—Al—O, Ti—Si—O, Ti—Al—Si—O, Ca—Al—O, and Ca—Si—Al—O.

6. A method for producing a light olefin product comprising converting syngas to the light olefin product in the presence of the catalyst of claim 1, wherein the light olefin product comprises ethylene.

7. The method according to claim 6, wherein the converting is conducted under a pressure of 0.5-10 MPa, reaction temperature of 300-600° C., a space velocity of 300-10000 h .sup.−1, the syngas is a H2/CO mixture with a molar ratio of H2/CO of 0.2-3.5.

8. The method according to claim 6, wherein the light olefin product comprises C.sub.2-4 olefin, and the method achieves a selectivity of the ethylene of 75-82%, a selectivity of a methane side product of less than 9%, and a selectivity of hydrocarbon products with more than 4 C atoms of less than 10%.

9. The catalyst according to claim 2, wherein the specific surface area of MnO.sub.x, ZnO.sub.x, CeO.sub.x, GaO.sub.x, BiO.sub.x and InO.sub.x is 50-100 m.sup.2/g, and the specific surface area of Mn.sub.aCr.sub.(1-a)O.sub.x, Mn.sub.aAl.sub.(1-a)O.sub.x, Mn.sub.aZr.sub.(1-a)O.sub.x, Mn.sub.aIn.sub.(1-a)O.sub.x, Zn.sub.aCr.sub.(1-a)O.sub.x, Zn.sub.aAl.sub.(1-a)O.sub.x, Zn.sub.aGa.sub.(1- a)O.sub.x, Zn.sub.aIn.sub.(1-a)O.sub.x, CO.sub.aAl.sub.(1-a)O.sub.x, Fe.sub.aAl.sub.(1-a)O.sub.x, In.sub.a Al.sub.bMn.sub.(1-a-b)O.sub.x, and In.sub.aGa.sub.bMn.sub.(1-a-b)O.sub.x is 50-150 m.sup.2/g.

10. The catalyst according to claim 3, wherein the weight ratio of the active ingredients ingredient in the component Ito the component II is 0.3-8.

11. The method according to claim 7, wherein the pressure is 1-8 MPa, the reaction temperature is 300° C. -450° C., the space velocity is 500-9000 h .sup.−1, the molar ratio of H2/CO is 0.3-2.5, and the syngas also comprises CO.sub.2, and a volume concentration of CO.sub.2 in the syngas is 0.1-50%.

12. The method according to claim 7, wherein the pressure is 2-8 MPa, and the space velocity is 500-6000 h.sup.−1.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(1) 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

(2) I. Preparation of Component I

(3) 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.

(4) The specific surface area of the sample can be tested through a physical adsorption method of nitrogen or argon.

(5) The metal oxide in the present invention can be obtained by purchasing a commercially available metal oxide with a high specific surface area, or obtained by the following methods:

(6) I. Preparation of Component I of Catalyst

(7) (I) ZnO material with high specific surface area was synthesized through a precipitation method:

(8) (1) 3 parts of 0.446 g (1.5 mmol) of Zn(NO.sub.3)2.6H2O were respectively weighed into three containers; 0.300 g (7.5 mmol), 0.480 g (12 mmol) and 0.720 g (18 mmol) of NaOH were respectively weighed and successively added to the above three containers; 30 ml of deionized water was weighed and added to the three containers; stirring was conducted for a time greater than 0.5 h at 70° C. to uniformly mix a solution; natural cooling was conducted to room temperature; reaction liquid was centrifugally separated to collect the centrifugally separated precipitate; and washing was conducted with deionized water twice to obtain ZnO metal oxide precursor;

(9) (2) roasting: after drying the obtained product in the air, the product was roasted in an atmosphere to obtain ZnO material with high specific surface area. The atmosphere is inert gas, reducing gas or oxidizing gas. The inert gas is one or more than one of N.sub.2, He and Ar. The reducing gas is one or two of H.sub.2 and CO, and the reducing gas may also contain the inert gas. The oxidizing gas is one or more than one of O.sub.2, O.sub.3 and NO.sub.2, and the oxidizing gas may also contain the inert gas. Roasting temperature is 300-700° C., and time is 0.5 h.sup.−12 h.

(10) The purpose of roasting is to decompose the precipitated metal oxide precursor into oxide nanoparticles with high specific surface area at high temperature, and clean the adsorbed species on the surface of the oxide generated by decomposition through the high temperature roasting treatment.

(11) Specific samples and preparation conditions thereof are shown in Table 1 below. As a reference example, ZnO #4 in the table is a commercially available ZnO single crystal with low specific surface area.

(12) TABLE-US-00001 TABLE 1 Preparation of ZnO Material and Parameter Performance Zinc Oxide Specific Sample Roasting Roasting Roasting Surface Number Time/h Temperature/° C. Atmosphere Area m.sup.2/g ZnO#1 5 500 Ar 71 ZnO#2 2 320 5% H2/N2 47 ZnO#3 3 550 Air 15 ZnO#4 — — <1

(13) (II) MnO material with high specific surface area was synthesized through a coprecipitation method:

(14) The preparation process is the same as that of the above ZnO #2. The difference is that, the precursor of Zn is changed for the corresponding precursor of Mn, which may be one of manganous nitrate, manganese chloride and manganese acetate, and is manganous nitrate herein. The corresponding product is defined as MnO. The specific surface area is 23 m.sup.2/g.

(15) (III) CeO.sub.2 material with high specific surface area was synthesized through a coprecipitation method:

(16) The preparation process is the same as that of the above ZnO #2. The difference is that, the precursor of Zn is changed for the corresponding precursor of Ce, which may be one of cerium nitrate, cerium chloride and cerous acetate, and is cerium nitrate herein. The corresponding product is defined as CeO.sub.2. The specific surface area is 92 m.sup.2/g.

(17) (IV) Ga.sub.2O.sub.3 material with high specific surface area was synthesized through a coprecipitation method:

(18) The preparation process is the same as that of the above ZnO #2. The difference is that, the precursor of Zn is changed for the corresponding precursor of Ga, which may be one of gallium nitrate, gallium chloride and gallium acetate, and is gallium nitrate herein. The corresponding product is defined as Ga.sub.2O.sub.3. The specific surface area is 55 m.sup.2/g.

(19) (V) Bi.sub.2O.sub.3 material with high specific surface area was synthesized through a coprecipitation method:

(20) The preparation process is the same as that of the above ZnO #2. The difference is that, the precursor of Zn is changed for the corresponding precursor of Bi, which may be one of bismuth nitrate, bismuth chloride and bismuth acetate, and is bismuth nitrate herein. The corresponding product is defined as Bi.sub.2O.sub.3. The specific surface area is 87 m.sup.2/g.

(21) (VI) In.sub.2O.sub.3 material with high specific surface area was synthesized through a coprecipitation method:

(22) The preparation process is the same as that of the above ZnO #2. The difference is that, the precursor of Zn is changed for the corresponding precursor of In, which may be one of indium nitrate, indium chloride and indium acetate, and is indium nitrate herein. The corresponding product is defined as In.sub.2O.sub.3. The specific surface area is 52 m.sup.2/g.

(23) (VII) Mn.sub.aCr.sub.(1−a)O.sub.x, Mn.sub.aAl.sub.(1−a)O.sub.x, Mn.sub.aZr.sub.(1−a)O.sub.x, Mn.sub.aIn.sub.(1−a)O.sub.x, Zn.sub.aCr.sub.(1−a)O.sub.x, Zn.sub.aAl.sub.(1−a)O.sub.x, Zn.sub.aGa.sub.(1−a)O.sub.x, Zn.sub.aIn.sub.(1−a)O.sub.x, Co.sub.aAl.sub.(1−a)O.sub.x, Fe.sub.aAl.sub.(1−a)O.sub.x, In.sub.aAl.sub.bMn.sub.(1−a−b)O.sub.x and In.sub.aGa.sub.bMn(1−a−b)O.sub.x with high specific surface area were synthesized through a precipitation method

(24) Zinc nitrate, aluminum nitrate, chromic nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate and ferric nitrate were adopted as precursors, and mixed at room temperature in water (wherein for ammonium carbonate as a precipitant, a feeding ratio is excessive or the ratio of ammonium ions to metal ions is preferably 1:1). The above mixed solution was aged, and then taken out for washing, filtering and drying; and the obtained solid was roasted under an air atmosphere to obtain a metal oxide with high specific surface area. Specific samples and preparation conditions thereof are shown in Table 2 below.

(25) TABLE-US-00002 TABLE 2 Preparation of Metal Oxide with High Specific Surface Area and Performance Parameters Feeding Ratio of Metal Elements and Final Molar Concentration of Aging Roasting Specific Metal One Metal in Temperature Aging Temperature Roasting Surface Oxide Water (mmol/L) ° C. Time h ° C. Time h Area m.sup.2/g ZnCr.sub.2O.sub.4 ZnCr = 1:2, Zn is 120 24 500 2 126 50 mM ZnAl.sub.2O.sub.4 ZnAl = 1:2, Zn is 130 20 400 4 137 50 mM ZnGa.sub.2O.sub.4 ZnGa = 1:2, Zn is 130 20 400 4 110 50 mM ZnIn.sub.2O.sub.4 ZnIn = 1:2, Zn is 130 20 400 4 87 50 mM MnCr.sub.2O.sub.4 MnCr = 1:2, Mn is 140 18 450 3 11 50 mM MnAl.sub.2O.sub.4 MnAl = 1:2, y = 145 16 400 2 15 2; and Mn is 50 mM MnZr2O.sub.4 MnZr = 1:2, Mn is 150 12 500 1 38 50 mM MnIn.sub.2O.sub.4 MnIn = 1:2, Mn is 150 12 500 1 67 50 mM CoAl.sub.2O.sub.4 CoAl = 1:2, Co is 145 16 400 2 22 50 mM FeAl.sub.2O.sub.4 FeAl = 1:2, Fe is 145 16 400 2 30 50 mM InAl3MnO.sub.7 In:A1:Mn = 1:3:1; 150 12 500 1 84 Mn is 50 mM InGa.sub.2MnO.sub.7 In:Ga:Mn = 1:2:1; 145 16 400 2 67 Mn is 50 mM

(26) (VIII) Metal oxide dispersed in dispersing agent Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2

(27) Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 dispersed metal oxide was prepared through a precipitate deposition method by taking Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 as a carrier. By taking preparation of dispersed ZnO as an example, commercial Cr.sub.2O.sub.3 (the specific surface area is about 5 m.sup.2/g), Al.sub.2O.sub.3 (the specific surface area is about 20 m.sup.2/g) or ZrO.sub.2 (the specific surface area is about 10 m.sup.2/g) as a carrier was dispersed in water in advance, and then mixed and precipitated at room temperature with a sodium hydroxide precipitant by taking zinc nitrate as raw material. The molar concentration of Zn.sup.2+ was 0.067M; and the ratio of molar fractions of Zn.sup.2+ and the precipitant was 1:8; and then aging was conducted at 160° C. for 24 hours to obtain dispersed ZnO by taking Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2 as the carrier (the contents of the dispersing agents in the component I are 0.1 wt %, 20 wt % and 85 wt %). The obtained sample was roasted at 500° C. for 1 hour in air. The products are successively defined as dispersed oxides 1-3, and the specific surface areas are successively 148 m.sup.2/g, 115 m.sup.2/g and 127 m.sup.2/g.

(28) The same method is used to obtain dispersed MnO oxide by taking SiO.sub.2 (the specific surface area is about 2 m.sup.2/g), Ga.sub.2O.sub.3 (the specific surface area is about 10 m.sup.2/g), or TiO.sub.2 (the specific surface area is about 15 m.sup.2/g) as the carrier (the contents of the dispersing agents in the component I are 5 wt %, 30 wt % and 60 wt %). The products are successively defined as dispersed oxides 4-6. The specific surface areas are successively 97 m.sup.2/g, 64 m.sup.2/g and 56 m.sup.2/g.

(29) The same method is used to obtain dispersed ZnO oxide by taking activated carbon (the specific surface area is about 1000 m.sup.2/g), graphene (the specific surface area is about 500 m.sup.2/g), or carbon nanotube (the specific surface area is about 300 m.sup.2/g) as the carrier (the contents of the dispersing agents in the component I are 5 wt %, 30 wt % and 60 wt %). The products are successively defined as dispersed oxides 7-9. The specific surface areas are successively 177 m.sup.2/g, 245 m.sup.2/g and 307 m.sup.2/g.

(30) II. Preparation of Component II (Zeolite of MOR Topology)

(31) The MOR topology is an orthorhombic crystal system, is of a one-dimensional porous channel structure with parallel elliptical straight-through porous channels, and includes 8-ring and 12-ring one-dimensional straight-through porous channels. 8-ring porous channel are communicated on the side edges of the 12-ring porous channels.

(32) The MOR zeolite in the present invention may be a commercial zeolite which is purchased directly or a synthesized zeolite. Herein, MOR zeolite produced by Nankai University Catalyst Plant is used as MOR1; meanwhile, seven zeolites with MOR topology are also prepared by taking hydrothermal synthesis as an example.

(33) The specific preparation process is:

(34) aluminum sulphate was mixed with a sodium hydroxide solution according to n(SiO.sub.2)/n(Al.sub.2O.sub.3)=15, n(Na.sub.2O)/n(SiO.sub.2)=0.2, n(H.sub.2O)/n(SiO.sub.2)=26; then, silica sol was added and stirred for 1 h to obtain homogeneous phase initial gel; then, the solution was transferred into a high pressure synthesis kettle, statically crystallized at 180° C. for 24 h, quenched, washed and dried to obtain a mordenite sample labeled as Na-MOR.

(35) Na-MOR was taken, mixed with 1 mol/L ammonium chloride solution, stirred at 90° C. for 3 h, washed, dried for four times in succession, and roasted at 450° C. for 6 h to obtain H-mordenite.

(36) The skeleton element composition of the zeolite of the MOR topology prepared by the above process may be one of Si—Al—O, Ga—Si—O, Ga—Si—Al—O, Ti—Si—O, Ti—Al—Si—O, Ca—Al—O and Ca—Si—Al—O.

(37) O element of part of the skeleton is connected with H, and corresponding products are successively defined as MOR1-8.

(38) TABLE-US-00003 TABLE 3 Preparation of Zeolite of MOR Topology and Performance Parameters Sample Al, Ga and Ti Hydrothermal Number Si and Ca Sources Sources Molar Ratio Temperature (° C.) Time (Day) MOR2 silica sol Ca(OH) Al(OH).sub.3 n(SiO.sub.2 + CaO)/n(Al.sub.2O.sub.3) = 11, 180 1 n(SiO.sub.2)/n(CaO) = 43, n(Na2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 26 MOR3 TEOS AlOOH n(SiO.sub.2)/n(AhO.sub.3 + Ga.sub.2O.sub.3) = 12, 170 1.3 gallium n(Ga.sub.2O.sub.3)/n(AhO.sub.3) = 7, nitrate n(Na2O)/n(SiO.sub.2) = 0.3 n(H.sub.2O)/n(SiO.sub.2) = 26 MOR4 silica sol titanium n(SiO.sub.2)/n(TiO.sub.2) = 40, 185 1 sol n(Na2O)/n(SiO.sub.2) = 0.3 n(H2O)/n(SiO.sub.2) = 26 MOR5 silica sol aluminum n(SiO.sub.2)/n(Al.sub.2O.sub.3) = 8, 185 1 sulfate n(Na2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 27 MOR6 silica sol aluminum n(SiO.sub.2)/n(Al.sub.2O3) = 12, 180 1.1 nitrate n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 23 MOR7 TEOS aluminum n(SiO.sub.2)/n(Al.sub.2O.sub.3) = 17, 175 1.5 sulfate n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 28 MOR8 silica sol titanium n(SiO.sub.2)/n(Al2O.sub.3 + TiO.sub.2) = 15, 175 0.7 sol n(TiO.sub.2)/n(AhO.sub.3) = 1, AlOOH n(Na.sub.2O)/n(SiO.sub.2) = 02n(H.sub.2O)/n (SiO.sub.2) = 25

(39) A proper quantity of the prepared zeolite was dehydrated and degassed under vacuum at temperature of 400° C. and pressure of 10−4 Pa. After 10 h, when the temperature was reduced to 300° C., 200 Pa of organic base gas was introduced into a vacuum chamber. After balance for 10 h, desorption was conducted at the same temperature for 1 h.

(40) MOR1, MOR2, MOR3, MOR4, MOR5, MOR6, MOR7 and MOR8 were treated with dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, 1,2-dimethylpropylamine, 1,2-propanediamine, 2-propeneamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutylamine, sec-butylamine, 1,4-butanediamine, tert-butylamine, diisobutylamine hexylamine, 2-ethylhexylamine, hexamethylenediamine and trioctylamine to respectively obtain MOR9, MOR10, MOR11, MOR12, MOR13, MOR14, MOR15, MOR16, MOR17, MOR18, MOR19, MOR20, MOR21, MOR22, MOR23, MOR24, MOR25, MOR26, MOR27, MOR28, MOR29, MOR30, MOR31 and MOR32.

(41) III. Catalyst Preparation

(42) The component I and the component II in the required ratio were added to the container to achieve the purposes of separation, crushing, uniform mixing and the like through one or more than two of extrusion force, impact force, shear force and friction force generated by high-speed motion of the material and/or the container, so as to realize conversion of 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.

(43) 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 selected from any of the following gas:

(44) a) nitrogen and/or inert gas;

(45) b) mixed gas of hydrogen, nitrogen and/or inert gas, with the volume of hydrogen in the mixed gas being 5-50%;

(46) c) mixed gas of CO, nitrogen and/or inert gas, with the volume of CO in the mixed gas being 5-20%;

(47) d) mixed gas of O.sub.2, nitrogen and/or inert gas, with the volume of O.sub.2 in the mixed gas being 5-20%, wherein the inert gas is one or more than one of helium, argon and neon.

(48) The mechanical mixing can adopt one or more than one of mechanical agitation, ball milling, rocking bed mixing and mechanical grinding for composition. Specifically:

(49) Mechanical stirring: mixing the component I and the component II with a stirring rod in a stirring tank; and regulating the mixing degree of the component I and the component II by controlling stirring time (5 min-120 min) and rate (30-300 r/min).

(50) Ball milling: rolling at high speed in a grinding tank by using abrasive and the catalysts; and producing strong impact and milling on the catalysts to achieve the effects of dispersing and mixing the component I and the component II. 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 range is 20-100:1) is controlled.

(51) Shaking table mixing: premixing the component I and the component II and placing the components into the container; realizing the mixing of the component I and the component II by controlling the reciprocating oscillation or circumferential oscillation of a shaking table; and realizing uniform mixing by regulating oscillation speed (range: 1-70 r/min) and time (range: 5 min-120 min).

(52) Mechanical grinding: premixing the component I and the component II and placing the components into the container; and under certain pressure (range: 5 kg-20 kg), making relative motion (speed range: 30-300 r/min) by an abrader and mixed catalysts to achieve the effect of uniform mixing. Specific catalyst preparation and parameter features are shown in Table 4.

(53) TABLE-US-00004 TABLE 4 Preparation of Catalysts and Parameter Features Compounding Mode and Condition Ball Milling Mechanical Abrasive Polishing Mechanical Material, Rocking Bed Pressure Agitation Size Oscillation (kg) and Weight Rate Range and Speed Relative Catalyst Component Component Ratio of (r/min) and Catalyst (r/min) and Movement Rate Number I II I to II Time (min) Mass Ratio Time (min) (r/min) A ZnO#1 MOR9 0.33 5, 30 B ZnO#2 MORIO 0.5 100, 250 C ZnO#3 MOR11 2 5 mm stainless steel ball, 50:1 D MnO MOR12 1 6 mm stainless steel ball, 60:1 E CeO.sub.2 MOR13 1 5, 10 F Bi2O.sub.3 MOR14 3 60, 100 G In.sub.2O.sub.3 MOR15 3 5, 30 H Ga.sub.2O.sub.3 MOR16 1 100, 300 I ZnCr.sub.2O.sub.4 MOR17 5 6 mm agate ball, 100:1 J ZnAl.sub.2O.sub.4 MOR18 1 70, 100 K ZnGa.sub.2O.sub.4 MOR19 3 15, 200 L Znln2O.sub.4 MOR20 0.33 20, 300 M MnCr.sub.2O.sub.4 MOR21 1 100, 300 N MnAl.sub.2O.sub.4 MOR22 3 6 mm quartz, 100:1 O MnZr2O.sub.4 MOR23 0.33 6 mm quartz, 100:1 P MnIn.sub.2O.sub.4 MOR24 1 10, 100 Q CoAl.sub.2O.sub.4 MOR25 1 5, 10 R FeAl.sub.2O.sub.4 MOR26 3 60, 100 S InA13MnO.sub.7 MOR27 3 5, 30 T InGa.sub.2MnO.sub.7 MOR28 1 100, 300 U dispersed MOR29 0.33 6 mm quartz, oxide 1 100:1 V dispersed MOR30 1 100, 250 oxide 2 W dispersed MOR31 3 5 mm oxide 3 stainless steel ball, 50:1 X dispersed MOR32 1 10, 100 oxide 4 Y dispersed MOR9 4 50, 60 oxide 5 Z dispersed MOR9 3 10, 100 oxide 6 Z1 dispersed MOR9 20 5 mm oxide 7 stainless steel ball, 100:1 Z2 dispersed MOR9 16 100, 200 oxide 8 Z3 dispersed MOR9 0.1 20, 100 oxide 9 Reference ZnO#4 MOR24 3 20, 30 example 1 Reference MnCr.sub.2O.sub.4 MORI 1 5, 10 example 2 Reference MnAl.sub.2O.sub.4 MOR2 1 5, 10 example 3 Reference MnZr2O.sub.4 MOR3 1 5, 10 example 4 Reference MnIn.sub.2O.sub.4 MOR4 1 5, 10 example 5 Reference CoAhO.sub.4 MOR5 1 5, 10 example 6 Reference FeAl.sub.2O.sub.4 MOR6 1 5, 10 example 7 Reference InA13MnO.sub.7 MOR7 1 5, 10 example 8 Reference InGa.sub.2MnO.sub.7 MOR8 1 5, 10 example 9 Reference composite MOR11 2 5 mm example 10 metal ZnCo, stainless the molar steel ball, ratio of Zn 50:1 to Co is 1:1. Reference TiO.sub.2 MOR11 2 5 mm example 11 stainless steel ball, 50:1

(54) Example of Catalytic Reactions

(55) A fixed bed reaction is taken as an example, but the catalyst is also applicable to a fluidized bed reactor. The apparatus was 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).

(56) 2 g of the above catalyst in the present invention was placed in a fixed bed reactor. The air in the reactor was replaced with Ar; and then the temperature was raised to 300° C. in the H.sub.2 atmosphere, and then the syngas (H2/CO molar ratio=0.2-3.5) was switched. The syngas can also include CO.sub.2, wherein the volume concentration of CO.sub.2 in the syngas is 0.1-50%. 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 300-10000 ml/g/h. On-line chromatography is used to detect and analyze the product.

(57) The reaction performance can be changed by changing the temperature, pressure and space velocity. The selectivity of the ethylene and the propylene in the product is as high as 78-87%, and the conversion rate of the raw material is 10-60%. Due to the effective synergy between the zeolite and the oxide, mass production of the methane and C.sub.4+ hydrocarbons is avoided.

(58) TABLE-US-00005 TABLE 5 Application and Effect of Catalysts Ethylene Space Time Ethylene and H2/CO Yield (mmol Propylene CH4 Ethylene C.sub.4+ GHSV Temperature MOLAR Pressure Olefin/h .Math. g Selectivities Selectivity Selectivity Selectivity Embodiment Catalyst (h.sup.−1) (° C.) RATIO (MPa) Catalyst) % % % % 1 A 3500 420 2.5 8 0.67 83 7 75 5 2 B 3000 480 1.5 3 0.63 81 5 76 6 3 C 4500 410 1 4 0.37 78 2 79 4 4 D 5000 370 3.5 9 0.32 79 3 76 8 5 E 3000 470 0.5 5 0.75 82 4 75 7 6 F 3500 410 2 4 0.68 82 4 76 8 7 G 3000 450 1 6 0.33 78 8 75 9 8 H 2500 360 1 5 0.38 78 9 75 9 9 I 7500 410 2.5 5 0.99 87 6 81 4 10 J 4000 350 3 7 1.11 86 4 81 3 11 K 3000 370 2.5 3 1.28 86 2 81 3 12 L 2500 350 3 3.5 0.79 83 5 76 6 13 M 3500 410 3.5 0.9 0.31 78 9 75 6 14 N 4000 400 2 2.5 0.34 78 9 76 6 15 O 2500 520 1 8 0.54 80 8 75 5 16 P 2500 400 3.5 1.5 0.73 83 7 76 3 17 Q 3000 400 0.5 7 0.51 79 7 76 5 18 R 3500 360 2.5 7.5 0.41 79 8 76 9 19 S 8500 350 2.5 5 0.67 85 5 82 5 20 T 1000 450 1 3.5 0.58 84 8 81 6 21 U 2500 410 1.5 7 0.93 87 3 75 5 22 V 3000 380 1 6 0.99 86 6 78 3 23 W 500 370 4 5 1.10 85 4 75 6 24 X 2500 350 2.5 5 1.08 86 6 75 4 25 Y 2000 410 1 7 1.05 86 2 81 4 26 Z 1500 430 2.5 3 0.99 86 3 77 4 27 Z1 4000 400 2 3.5 0.13 78 8 75 7 28 Z2 3000 430 3.5 0.9 0.11 79 7 75 8 29 Z3 10000 370 2 2.5 0.12 78 9 75 7 30 J 2500 370 1.5 (CO.sub.2 5 0.99 85 7 80 5 concentration of 1%) 31 K 4000 370 1 (CO.sub.2 7 0.90 87 5 83 4 concentration of 45%) 32 Reference 1000 300 0.5 1 0.02 35 55 20 3 example 1 33 Reference 1000 430 1 2 0.47 80 7 75 10 example 2 34 Reference 4000 450 3 3 0.28 80 6 75 11 example 3 35 Reference 2000 350 2.5 3 0.35 81 6 76 9 example 4 36 Reference 2000 400 0.5 7 0.37 75 6 73 15 example 5 37 Reference 2000 360 2.5 2.5 0.31 76 11 75 10 example 6 38 Reference 2000 400 1 4 0.59 80 11 75 7 example 7 39 Reference 2000 370 0.5 9 0.54 80 10 75 6 example 8 40 Reference 3000 470 3 3 0.30 80 10 75 7 example 9 41 Reference 3000 450 2 4 0.53 18 32 10 40 example 10 42 Reference 2000 450 1 6 0.01 21 66 7 5 example 11 43 Reference 3000 450 2.5 4 <0.01 1.2 50 0.8 1.1 example 12 44 Reference 2200 450 3 2 <0.01 — — — — example 13

(59) The reaction results of reference examples 2-9 show that MOR which is post-processed by the fatty amine has a significant effect on the regulation of catalytic performance. Compared with the catalysts which are not regulated with the fatty amine, the regulated catalyst significantly reduces the selectivity of the methane and hydrocarbons above C.sub.4 and also improves the selectivity of the light olefin and the ethylene.

(60) The component I in the catalyst adopted in reference example 10 is metal ZnCo. The molar ratio of ZnCo is 1:1. Other parameters and the mixing process are the same as those of catalyst C.

(61) The component I in the catalyst adopted in reference example 11 is TiO.sub.2. Other parameters and the mixing process are the same as those of catalyst C.

(62) The catalyst adopted in reference example 12 is a sample containing only component I ZnO #1 without the MOR zeolite, and the reaction conversion rate is very low. The products mainly comprise by-products such as dimethyl ether and methane, and almost no ethylene is produced.

(63) The catalyst adopted in reference example 13 is a metal oxide containing only MOR9 zeolite of component II without the component I and acting as an active ingredient, and the catalytic reaction almost has no activity.

(64) Reference examples 12 and 13 indicate that reaction effects are extremely poor when only component I or component II exists, and do not have the excellent reaction performance in the present invention.

(65) The above embodiments are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the present invention is defined by the appended claims. Various equivalent replacements and amendments made without departing from the spirit and the principle of the present invention shall be covered within the scope of the present invention.