Catalyst and method for preparing light olefin using direct conversion of syngas

Abstract

A catalyst for preparing light olefin using direct conversion of syngas is a composite catalyst and formed by compounding component I and component II in a mechanical mixing mode. The active ingredient of component I is a metal oxide; and the component II is one or more than one of zeolite of CHA and AEI structures or metal modified CHA and/or AEI zeolite. A weight ratio of the active ingredients in the component I to the component II is 0.1-20. The reaction process has high product yield and selectivity, wherein the sum of the selectivity of the propylene and butylene reaches 40-75%; and the sum of the selectivity of light olefin comprising ethylene, propylene and butylene can reach 50-90%. Meanwhile, the selectivity of a methane side product is less than 15%.

Claims

1. A catalyst, comprising a component I and a component II, which are compounded in a mechanical mixing mode; an ingredient of the component I being a metal oxide; the component II being a zeolite of CHA or AEI topology; 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.aAl.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; 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, CoaAl.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; the zeolite of CHA or AEI topology comprises eight-membered ring orifices, a three-dimensional porous channel, and CHA cage; and the zeolite of CHA or AEI topology comprises mediate strong acid sites in an amount of 0.003-0.06 mol/kg.

2. The catalyst according to claim 1, wherein the skeleton element composition of the zeolite of CHA or AEI topology is at least one of Si—O, Si—Al—O, Si—Al—P—O, Al—P—O, Ga—P—O, Ga—Si—Al—O, Zn—Al—P—O, Mg—Al—P—O, and Co—Al—P—O.

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

4. The catalyst according to claim 1, wherein the dispersing agent is also added to the component I; the metal oxide is dispersed in the dispersing agent; 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; in the component I, the content of the dispersing agent is 0.05-90 wt %, and the balance is the metal oxide.

5. The catalyst according to claim 1, wherein H is connected or not connected to O element of the zeolite skeleton.

6. The catalyst according to claim 5, wherein, when H is connected to O element of the zeolite skeleton, the H is entirely or partially replaced by at least 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.

7. A method for preparing light olefin via direct conversion of syngas comprising converting the syngas to the light olefin in the presence of the catalyst of claim 1.

8. The method according to claim 7, wherein the converting is conducted under a pressure of 0.5-10 MPa, a reaction temperature of 300-600° C., and a space velocity of 300-12000 h.sup.−1, and the syngas is a H.sub.2/CO mixture with a ratio of H.sub.2/CO of 0.2-3.5.

9. The method according to claim 7, wherein the light olefin is C.sub.2-4 olefin, and the method achieves a selectivity for C.sub.2-4 olefin of 50-90%, and a selectivity for a methane side product of lower than 15%.

10. The catalyst according to claim 1, 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, CoaAl.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 50-150 m.sup.2/g.

11. The catalyst according to claim 3, wherein the weight ratio of the ingredients in the component I to the component II is 0.3-5.

12. The method according to claim 7, wherein the converting is conducted under a pressure of 1-8 MPa; a reaction temperature of 350° C.-450° C., and a space velocity of 1000-9000 h.sup.−1, and the syngas is a H.sub.2/CO mixture with a ratio of H.sub.2/CO of 0.3-2.5.

13. The method according to claim 12, wherein the space velocity is 3000-9000 h.sup.−1.

14. The catalyst according to claim 1, wherein the skeleton element composition of the zeolite of CHA or AEI topology is at least one of Si—Al—P—O, Al—P—O, Ga—P—O, Zn—Al—P—O, Mg—Al—P—O, and Co—Al—P—O.

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 does not mean that the conditions must be satisfied to achieve the purpose.

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

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

(4) I. Preparation of Component I of Catalyst

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

(6) (1) 3 parts of 0.446 g (1.5 mmol) of Zn(NO.sub.3).sub.2.6H.sub.2O 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;

(7) (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-12 h.

(8) 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.

(9) 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.

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

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

(12) 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.

(13) (III) CeO.sub.2 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 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.

(15) (IV) Ga.sub.2O.sub.3 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 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.

(17) (V) Bi2O.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 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.

(19) (VI) In.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 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.

(21) (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.sub.(1-a-b)O.sub.x with high specific surface area were synthesized through a precipitation method:

(22) 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 is 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.

(23) TABLE-US-00002 TABLE 2 Preparation of Metal Oxide with High Specific Surface Area and Performance Parameters Feeding Ratio of Metal Specific Elements and Final Molar Aging Surface Concentration of One Aging Time Roasting Roasting Area Metal Oxide Metal in Water (mmol/L) Temperature° C. h Temperature° C. Time h m.sup.2/g ZnCr.sub.2O.sub.4 ZnCr = 1:2, and Zn is 50 mM 120 24 500 2 126 ZnAl.sub.2O.sub.4 ZnAl = 1:2, and Zn is 50 mM 130 20 400 4 137 ZnGa.sub.2O.sub.4 ZnGa = 1:2, and Zn is 130 20 400 4 110 50 mM ZnIn.sub.2O.sub.4 Znln = 1:2, and Zn is 50 mM 130 20 400 4 87 MnCr.sub.2O.sub.4 MnCr = 1:2, and Mn is 140 18 450 3 11 50 mM MnAl.sub.2O.sub.4 MnAl = 1:2, y = 2; and Mn is 145 16 400 2 15 50 mM MnZr.sub.2O.sub.4 MnZr = 1:2, and Mn is 150 12 500 1 38 50 mM MnIn.sub.2O.sub.4 Mnln = 1:2, and Mn is 150 12 500 1 67 50 mM CoAl.sub.2O.sub.4 CoAl = 1:2, and Co is 50 mM 145 16 400 2 22 FeAl.sub.2O.sub.4 FeAl = 1:2, and Fe is 50 mM 145 16 400 2 30 InA1.sub.3MnO.sub.7 In:A1:Mn = 1:3:1; and Mn 150 12 500 1 84 is 50 mM InGa.sub.2MnO.sub.7 In:Ga:Mn = 1:2:1; and Mn is 145 16 400 2 67 50 mM

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

(25) 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. The preparation of dispersed ZnO was taken as an example (the specific surface area is about 5 m.sup.2/g)

(26) Commercial Cr.sub.2O.sub.3, 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+ is 0.067M; and the ratio of molar fractions of Zn.sup.2+ and the precipitant is 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 were successively defined as dispersed oxides 1-3, and the specific surface areas were successively 148 m.sup.2/g, 115 m.sup.2/g and 127 m.sup.2/g.

(27) 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.

(28) 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. II. Preparation of component II (zeolite of CHA and AEI topology):

(29) The CHA and AEI topology has eight-membered ring orifices and a three-dimensional porous channel and comprises cha cage.

(30) The mediate strong acid described in the present invention can be tested by solid nuclear magnetic H spectrum, NH.sub.3-TPD, infrared ray and chemical titration. However, the test method of the acidity is not limited to the above test methods.

(31) The zeolite in the present invention may be the zeolite of CHA and AEI topology having acid density that satisfies the requirements of the present invention, and may also be the zeolite prepared according to the method reported in the existing literature (Chemcatchem, 2012, 4, 1428-1435). The present invention takes the zeolite prepared by a hydrothermal synthesis method as an example.

(32) 1) The specific preparation process is as follows:

(33) The raw materials of 30% (mass concentration) of silica sol, AlOOH, phosphoric acid, TEA® and deionized water were weighed according to 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, 0.5 time of molar weight of auxiliary HF was added to a template agent; the mixture was stirred and aged at 30° C. and then transferred into a hydrothermal reactor after 2 h, and crystallized at 200° C. for 24 h. The water bath was quenched to room temperature. Centrifugal washing was conducted repeatedly so that the pH of the supernatant is 7 at the end of washing. After the precipitate was dried at 110° C. for 17 h, the precipitate was calcined in air at 600° C. for 3 h to obtain the silicon-phosphorus-aluminum inorganic solid acid with hierarchical pore structure.

(34) The skeleton element composition of the zeolite of CHA and AEI topologies may be one or more than two of Si—O, Si—Al—O, Si—Al—P—O, Al—P—O, Ga—P—O, Ga—Si—Al—O, Zn—Al—P—O, Mg—Al—P—O and Co—Al—P—O.

(35) O element of part of the skeleton is connected with H, and corresponding products are successively defined as parts 1-7.

(36) TABLE-US-00003 TABLE 3 Preparation of Zeolite of CHA or AEI Topology and Performance Parameters Zeolite Acid Sample Si Aluminum Template Hydrothermal Amount Number Source Source p Source Agent Auxiliary Mass Ratio Temperaturer/° C. Time/day mol/kg part 1 TEOS sodium phosphoric TEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 180 1 025 metaaluminate acid R:H.sub.2O = 1.6:16:32: 55:150 part 2 silica A1(OH).sub.3 phosphoric Mor HC1 SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 150 4 027 sol acid R:H.sub.2O = 2.4:19:30: 15:150 part 3 TEOS A1O phosphoric TEAOH HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 160 4 0.13 OH acid R:H.sub.2O = 0.7:15: 32:55:150 part 4 silica aluminum phosphoric DIPEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 170 2.5 023 sol isopropoxide acid R:H.sub.2O = 1.1:17:32: 55:150 part 5 aluminum phosphoric TEAOH HF Al.sub.2O.sub.3:H.sub.3PO.sub.4:R: 190 1 0.006 sulfate acid H.sub.2O = 16:32:55: 150 part 6 silica aluminum phosphoric DIPEA SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 200 1 0.078 sol nitrate acid R:H.sub.2O = 0.5:17:32: 55:150 part 7 TEOS aluminum phosphoric TEA HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 170 0.7 0.055 sulfate acid R:H.sub.2O = 0.3:18: 32:55:150 part 8 aluminum phosphoric TEA HC1 Al.sub.2O.sub.3:H.sub.3PO.sub.4:R: 160 3.5 0.014 nitrate acid H.sub.2O = 11:32:55: 150

(37) 2) The H connected to the O element of skeletons of the above products 1-8 is replaced by the following metal ion parts: Na, Ca, K, Mg, Ge, Zr, Zn, Cr, Ga, Sn, Fe, Co, Mo and Mn by ion exchange; and the preparation process is:

(38) The above samples of parts 1-8 were taken and then mixed with 0.5 mol/L of metal ion nitrate solution to be exchanged according to the solid-liquid mass ratio of 1:30. The mixture was stirred at 80° C. for 6 h, washed, dried twice continuously, and roasted at 550° C. for 3 h to obtain CHA or AEI after metal ion exchange.

(39) Corresponding products are successively defined as parts 9-22.

(40) TABLE-US-00004 TABLE 4 Preparation of Zeolite of CHA or AEI Topology and Performance Parameters Zeolite Sample Ratio of metal Zeolite to be Exchange Acid Amount Number Ion ion and O Exchanged Temperature/° C. Time/h mol/kg part 9 Na 0.04 part 1 80 8 0.23 part 10 Ca 0.02 part 2 90 7 0.03 part 11 K 0.01 part 3 80 7 0.11 part 12 Mg 0.015 part 4 90 5 0.08 part 13 Ge 0.075 part 5 80 7 0.15 part 14 Zr 0.03 part 6 90 7 0.05 part 15 Zn 0.005 part 7 80 8 0.10 part 16 Cr 0.07 part 8 70 3 0.25 part 17 Ga 0.01 part 1 80 6 0.17 part 18 Sn 0.001 part 2 60 5 0.27 part 19 Fe 0.0005 part 3 70 5 0.23 part 20 Co 0.0003 part 4 80 6 0.18 part 21 Mo 0.0005 part 5 70 3 0.28 part 22 Mn 0.002 part 6 70 8 0.29

(41) 3) Zeolite composed of other elements

(42) TABLE-US-00005 Acid Sample Template Hydrothermal Time Amount Number Precursor 1 Precursor 2 Precursor 3 Agent Auxiliary Mass Ratio Temperature (° C.) (Day) mol/kg part 23 TEOS TEA HF SiO.sub.2:R:H.sub.2O = 1.6: 180 1 0.004 55:150 part 24 silica sol A1(0H).sub.3 Mor HF SiO.sub.2:Al.sub.2O.sub.3:R:H.sub.2O = 150 4 0.11 2.4:19:15:150 part 25 gallium phosphoric TEAOH HF Ga.sub.2O.sub.3:H.sub.3PO.sub.4:R: 160 4 0.012 nitrate acid H.sub.2O = 15:32:55:150 part 26 silica sol gallium phosphoric TEA HF SiO.sub.2:Ga.sub.2O.sub.3: 170 2.5 0.07 nitrate acid H.sub.3PO.sub.4:R:H.sub.2O = 1.1: 17:32:55:150 part 27 zinc nitrate aluminum phosphoric TEAOH HF ZnO:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 190 1 0.0506 sulfate acid R:H.sub.2O = 0.5:16:32: 55:150 part 28 magnesium aluminum phosphoric TEA MgO:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 200 1 0.178 nitrate nitrate acid R:H.sub.2O = 0.5:17: 32:55:150 part 29 cobalt aluminum phosphoric TEA HF SiO.sub.2:Al.sub.2O.sub.3:H.sub.3PO.sub.4: 170 0.7 0.255 nitrate sulfate acid R:H.sub.2O = 0.4:18:32: 55:150

(43) III. Catalyst Preparation

(44) 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.

(45) 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:

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

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

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

(49) 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.

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

(51) 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).

(52) 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.

(53) 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).

(54) 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.

(55) Specific catalyst preparation and parameter features are shown in Table 6.

(56) TABLE-US-00006 TABLE 6 Preparation of Catalysts and Parameter Features Compounding Mode and Condition Ball Milling Rocking Mechanical Mechanical Abrasive Bed Polishing Agitation Material, Size Oscillation Pressure (kg) Weight Rate (r/min) Range and Speed and Relative Catalyst Component Component Ratio of and Time Catalyst Mass (r/min) and Movement Number I II A to B (min) Ratio Time (min) Rate (r/min) A ZnO#1 part 1 0.33 5, 30 B ZnO#2 part 2 0.5 100, 250 C ZnO#3 part 3 2 5 mm stainless steel ball, 50:1 D MnO part 4 1 6 mm stainless steel ball, 60:1 E CeO.sub.2 part 5 1 5, 10 F Bi.sub.2O.sub.3 part 6 3 60, 100 G In.sub.2O.sub.3 part 7 3 5, 30 H Ga.sub.2O.sub.3 part 8 1 100, 300 I ZnCr.sub.2O.sub.4 part 9 5 6 mm agate ball, 100:1 ZnAl.sub.2O.sub.4 part 10 1 70, 100 K ZnGa.sub.2O.sub.4 part 11 3 15, 200 L ZnIn.sub.2O.sub.4 part 12 0.33 20, 300 M MnCr.sub.2O.sub.4 part 13 1 100, 300 N MnAl.sub.2O.sub.4 part 14 3 6 mm quartz, 100:1 O MnZr.sub.2O.sub.4 part 15 0.33 6 mm quartz, 100:1 P MnIn.sub.2O.sub.4 part 16 1 10, 100 Q CoAl.sub.2O.sub.4 part 17 1 100, 250 R FeAl.sub.2O.sub.4 part 18 3 5 mm stainless steel ball, 50:1 S InA1.sub.3MnO.sub.7 part 19 1 10, 100 T InGa.sub.2MnO.sub.7 part 20 4 50, 60 U dispersed part 21 3 10, 100 oxide 1 V dispersed part 22 20 5 mm oxide 2 stainless steel ball, 100:1 W dispersed part 23 0.5 5, 30 oxide 3 X dispersed part 24 1 100, 250 oxide 4 Y dispersed part 25 3 5 mm oxide 5 stainless steel ball, 50:1 Z dispersed part 26 1.5 6 mm oxide 6 stainless steel ball, 60:1 Z1 dispersed part 27 2.5 5, 10 oxide 7 Z2 dispersed part 28 1.5 60, 100 oxide 8 Z3 dispersed part 29 2 5, 30 oxide 9 Reference ZnO#4 part 1 3 20, 30 example 1 Reference composite part 3 2 5 mm example 2 metal ZnCo, stainless steel the molar ball, 50:1 ratio of Zn to Co is 1:1. Reference TiO.sub.2 part 3 2 5 mm example 3 stainless steel ball, 50:1

(57) Example of Catalytic Reactions

(58) A fixed bed reaction was taken as an example, but the catalyst was 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).

(59) 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 (H.sub.2/CO molar ratio=0.2-3.5) was switched. The pressure of the syngas was 0.5-10 MPa. The temperature was raised to reaction temperature of 300-600° C., and the air velocity of the reaction raw gas was regulated to 300-12000 ml/g/h. On-line chromatography was used to detect and analyze the product.

(60) 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 of propylene and butylene selectivity is 30-75%. The sum of selectivity of the lower alkene, the ethylene, the propylene and the 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 not be avoided, and the selectivity of the methane is low. Table 7 lists specific application and effect data of the catalysts.

(61) TABLE-US-00007 TABLE 7 Specific Application and Effect Data of Catalysts H.sub.2/CO CO CH.sub.4 Propylene and Temperature Molar Pressure Conversion Light Olefin Selectivity Butylene Embodiment Catalyst GHSV(h.sup.−1) (° C.) Ratio (MPa) Rate % Selectivity % % Selectivities % 1 A 3000 400 2.5 5 33.6 61.8 13.8 37.1 2 B 4000 410 1.5 9 27.5 62.7 8.4 42.0 3 C 4000 380 3 2.5 41.9 71.4 7.6 57.4 4 D 7000 420 1 10 24.5 74.7 11.8 60.1 5 E 2000 390 3.5 6 20.2 85.6 4.7 70.3 6 F 2000 410 1.5 3 40.3 78.4 8.5 67.7 7 G 3500 390 3.5 2.5 35.1 83.2 5.4 72.2 8 H 1500 370 2.5 5 19.6 85.1 4.5 74.7 9 I 2500 380 3 3.5 42.0 65.0 13.2 47.5 10 J 2000 410 2.5 8 23.3 84.7 6.4 71.4 11 K 2000 400 2.5 3 45.0 77.2 8.3 66.1 12 L 10500 520 0.5 1 35.4 76.0 10.6 64.6 13 M 3000 480 0.5 2 41.7 78.4 11.2 63.7 14 N 3000 470 0.5 2 30.4 80.0 7.4 70.8 15 O 3000 450 1 3 34.8 70.9 11.2 66.2 16 P 3000 450 1.5 3 43.5 65.7 14.8 43.5 17 Q 3000 350 3.5 5 33.0 62.2 9.6 44.7 18 R 2000 350 3 7 38.6 59.3 11.9 40.9 19 S 2500 400 1 6 19.0 60.8 11.7 45.7 20 T 4000 400 2 4 30.1 76.2 9.5 51.4 21 U 3000 400 3 3 36.1 67.5 11.1 43.3 22 V 8000 450 0.5 2 51.1 53.0 14.3 44.6 23 W 2000 410 2 3.5 11.7 85.3 2.9 75.0 24 X 3000 380 3.5 6 35.6 74.4 7.1 61.0 25 Y 5000 390 3 2.5 25.7 88.9 2.5 71.1 26 Z 4000 370 2 10 28.2 86.7 3.7 73.3 27 Z1 10000 470 1 1.5 12.7 85.1 10.8 72.7 28 Z2 2000 400 3.5 7 26.8 67.7 12.3 45.7 29 Z3 3000 380 1.5 2.5 41.3 55.3 14.2 43.1 38 Reference 3000 320 0.5 1 1.9 31.0 31.0 29.2 example 1 39 Reference 4000 450 3 3 30.5 26.8 22.6 12.9 example 2 40 Reference 2000 350 2.5 3 0.3 25.5 65.1 19.4 example 3 41 Reference 2000 410 1.5 3 24.6 46.2 9.7 25.6 example 4 42 Reference 3000 400 2 3.5 31.2 19.5 10.8 12.7 example 5 43 Reference 3000 450 2.5 4 8.3 1.5 50 0.7 example 6 44 Reference 2200 450 3 2 <1 — — — example 7
In reference example 1, the catalyst component I is ZnO#4, and component II is part 1. The zeolite in the catalyst adopted in reference example 4 is a commodity SAPO-34 purchased from Nankai University Catalyst Factory, wherein the temperature of desorption peak of mediate strong acid on NH3-TPD is 390° C. and the amount of the mediate strong acid sites is 0.6 mol/kg. The zeolite in the catalyst adopted in reference example 5 is a commodity ZSM-5 purchased from Nankai University Catalyst Factory, wherein the zeolite is of a full microporous structure, and the silica alumina ratio is 30.

(62) Reaction results of reference examples 4 and 5 show that, the topology and acid strength of CHA or AEI are crucial to the selective modulation of the products.

(63) The catalyst adopted in reference example 6 is a sample containing only component IZnO#1 without the 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.

(64) The catalyst adopted in reference example 7 is a sample containing only component II and part 1 zeolite without the component I, and the catalytic reaction almost has no activity.

(65) Reference examples 6 and 7 have extremely poor reaction effects when only containing component I or component II on the surface, and do not have the excellent reaction performance described in the present invention.

(66) In the reference technology of the document (Jiao et al., Science 351 (2016) 1065-1068), the acid amount of the used SAPO-34 zeolite is large. The acid amount of the mediate strong acid reaches 0.32 mol/kg according to the NH3-TPD test. Therefore, when the conversion rate is increased to 35%, alkene selectivity is 69%, alkane selectivity is 20%, alkene/alkane ratio is decreased to 3.5 and propylene and butylene selectivity is 40-50%.

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