METHOD FOR PREPARING LIGHT OLEFIN THROUGH CATALYTIC SYNGAS WITH HIGH SELECTIVITY BY HETEROATOM-DOPED ZEOLITE

Abstract

A composite catalyst containing heteroatom-doped zeolite for preparing light olefin using direct conversion of syngas 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 a heteroatom-doped zeolite. The zeolite topology is CHA or AEI, and the skeleton atoms include Al—P—O or Si—Al—P—O; the heteroatoms is at least one of divalent metal Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo, Cd, Ba and Ce, trivalent metal Ti and Ga, and tetravalent metal Ge. A weight ratio of the active ingredient in the component I to the component II is 0.1-20. The reaction process has high light olefin selectivity; the sum selectivity of the light olefin including ethylene, propylene and butylene can reach 50-90%, while the selectivity of a methane side product is less than 7%.

Claims

1. A catalyst comprising a component I and a component II, wherein an active ingredient of the component I is a metal oxide, and the component II is a heteroatom-doped zeolite; 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, 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, and In.sub.aGa.sub.bMn.sub.(1-a-b)O.sub.x, a value range of x is 0.7-3.7; a value range of a is 0-1; and a value range of a+b is 0-1; the zeolite is a zeolite with CHA or AEI topology, whose skeleton atoms comprise Al—P—O or Si—Al—P—O; the heteroatom is at least one of divalent metal Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo, Cd, Ba and Ce, trivalent metal Ti and Ga, and tetravalent metal Ge; the heteroatom-doped zeolite means that the heteroatom is doped in a zeolite skeleton to replace Al, P or Si in the zeolite skeleton.

2. The catalyst according to claim 1, wherein 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, 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, 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.

3. The catalyst according to claim 1, wherein a ratio of the sum of the molar weight of the heteroatoms in the heteroatom-doped zeolite to the molar weight of P is 0.001-0.6.

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

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

6. The catalyst according to claim 1, wherein the heteroatom-doped zeolite is prepared by an in-situ hydrothermal growth method or a post-treatment method; the in-situ hydrothermal growth method comprises the following steps: (1) preparation of a sol precursor: Al—P—O skeleton: dissolving a certain proportion of aluminum source and phosphorus source in water and stirring evenly; then adding a heteroatom-containing precursor and a template agent and stirring for 0.5-12 h; Si—Al—P—O skeleton: dissolving a certain proportion of aluminum source, phosphorus source and silicon source in water and stirring evenly; then adding the heteroatom-containing precursor and the template agent and stirring for 0.5-12 h; (2) hydrothermal crystallization: crystallizing the sol precursor obtained in step (1) at 160-200° C. for 4-7 days; (3) separation and washing: centrifuging, washing and drying the product after the crystallization reaction; (4) drying and roasting: roasting the product of step (3) at 550-600° C. for 3-6 h, wherein a molar ratio of the heteroatoms in the heteroatom precursor to the phosphorus source is 0-0.6; the post-treatment method comprises: Al—P—O skeleton: configuring a solution of the heteroatom precursor; impregnating AlPO-18 or AlPO-34 zeolite into the solution of the heteroatom precursor; drying the solution; finally roasting the solution at 550-600° C. for 3-6 h; Si—Al—P—O skeleton: configuring a solution of the heteroatom precursor; impregnating SAPO-18 or SAPO-34 zeolite into the solution of the heteroatom precursor; drying the solution; and finally roasting the solution at 550-600° C. for 3-6 h.

7. The catalyst according to claim 6, wherein the aluminum source is boehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate, or aluminum isopropoxide; the phosphorus source is phosphoric acid; the silicon source is silica sol, TEOS, white carbon black, quartz sand, or silicate; the heteroatom precursor is metal nitrate, sulfate, acetate, halide or oxide of a corresponding metal atom; the template agent is triethylamine or diisopropylethylamine.

8. A method for preparing light olefin through catalytic syngas with high selectivity comprising subjecting the syngas to a conversion reaction on a fixed bed or a moving bed to prepare light olefin in the presence of the catalyst of claim 1.

9. The method according to claim 8, wherein the conversion reaction is conducted at a pressure of the syngas of 0.5-10 MPa, a reaction temperature of 300-600° C., a space velocity of 300-10000 h.sup.−1, and wherein the syngas is a mixed gas of H.sub.2/CO with a molar ratio of Hz/CO of 0.2-3.5.

10. The method according to claim 9, wherein C.sub.2-4 olefin is prepared using one-step direct conversion of syngas; a selectivity for C.sub.2-4 olefin is 50-90%; and a selectivity for a methane side product is lower than 7%.

11. The catalyst according to claim 1, wherein 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 50-100 m.sup.2/g; and 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, 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, 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 50-150 m.sup.2/g.

12. The catalyst according to claim 1, wherein a weight ratio of the active ingredient in the component I to the component II is 0.3-5.

13. The method according to claim 8, wherein the conversion reaction is conducted at a pressure of the syngas of 1-8 MPa, a reaction temperature of 370-450° C., and a space velocity of 500-9000 h.sup.−1, and wherein the syngas is a mixed gas of H.sub.2/CO with a molar ratio of H.sub.2/CO of 0.3-2.5.

14. The method according to claim 8, wherein the conversion reaction is conducted at a pressure of the syngas of 2-8 MPa and a space velocity of 1000-6000 h.sup.−1.

15. The method according to claim 8, wherein the syngas contains CO.sub.2, and a volume concentration of CO.sub.2 in the syngas is 0.1-50%.

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0033] The present invention is further illustrated below through 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.

[0034] The specific surface area of the sample can be tested through a physical adsorption method of nitrogen or argon.

[0035] 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:

I. Preparation of Component I of Catalyst

[0036] (I) Synthesizing ZnO material with high specific surface area through a precipitation method:

[0037] (1) 3 parts of 0.446 g (1.5 mmol) of Zn(NO.sub.3).sub.2.Math.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; the mixture was stirred for more than 0.5 h at 70° C. to uniformly mix the solution; and the solution was naturally cooled to room temperature. Reaction liquid was centrifugally separated to collect the centrifugally separated precipitate; and the precipitate was washed with deionized water twice to obtain ZnO metal oxide precursor.

[0038] (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.

[0039] 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.

[0040] 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.

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

[0041] (II) Synthesizing MnO material with high specific surface area through a coprecipitation method:

[0042] 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.

[0043] (III) Synthesizing CeO.sub.2 material with high specific surface area through the coprecipitation method:

[0044] 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.

[0045] (IV) Synthesizing Ga.sub.2O.sub.3 material with high specific surface area through a coprecipitation method:

[0046] 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.

[0047] (V) Synthesizing Bi.sub.2O.sub.3 material with high specific surface area through a coprecipitation method:

[0048] 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.

[0049] (VI) Synthesizing In.sub.2O.sub.3 material with high specific surface area through a coprecipitation method:

[0050] 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.

[0051] (VII) Synthesizing 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 through a precipitation method:

[0052] 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.

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 Specific Concentration of Aging Roasting Surface One Metal in Water, Temperature Aging Temperature Roasting Area Metal Oxide mmol/L ° C. Time h ° C. Time h m.sup.2/g ZnCr.sub.2O.sub.4 ZnCr = 1:2, 120 24 500 2 126 Zn is 50 mM ZnAl.sub.2O.sub.4 ZnAl = 1:2, 130 20 400 4 137 Zn is 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 = 2; 145 16 400 2 15 and Mn is 50 mM MnZr.sub.2O.sub.4 MnZr = 1:2, Mn is 150 12 500 1 38 50 mM MnIn.sub.2O.sub.4 MnIn = 1:2, Mn is 50 150 12 500 1 67 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 50 145 16 400 2 30 mM InAlMnO.sub.7 In:Al:Mn = 1:3:1; 150 12 500 1 84 Mn is 50 mM InGaMnO.sub.7 In:Ga:Mn = 1:2:1; 145 16 400 2 67 Mn is 50 mM

[0053] (VIII) Metal Oxide Dispersed in Dispersant Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2

[0054] 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+ 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 dispersants 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 are successively 148 m.sup.2/g, 115 m.sup.2/g and 127 m.sup.2/g.

[0055] 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.

[0056] 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

[0057] The CHA and AEI topology has eight-membered ring orifices and a three-dimensional porous channel.

[0058] (I) Zeolite Prepared by Hydrothermal Synthesis

[0059] The specific preparation process is as follows:

[0060] Component II: taking MgAPO as an example, the raw materials of magnesium nitrate, aluminum hydroxide, phosphoric acid, diisopropylethylamine (DIPEA) and deionized water were weighed according to oxide MgO: Al.sub.2O.sub.3: P.sub.2O.sub.5:R:H.sub.2O=0.3:0.9:1:1.8:45 (molar ratio); the mixture was stirred and aged at 30° C., then transferred into a hydrothermal reactor after 2 h, and crystallized at 180° C. for 120 h. The mixture was cooled to room temperature. Centrifugal washing was conducted repeatedly so that the pH of the supernatant was 7 at the end of washing. After the precipitate was dried at 110° C. for 17 h, the precipitate was roasted in air at 600° C. for 3 h to obtain Mg-doped atomic zeolite.

TABLE-US-00003 TABLE 3 Preparation of Heteroatom-Doped Zeolite of CHA or AEI Topology and Performance Parameters Zeolite Molar Ratio Hydrothermal Sample Aluminum Template Heteroatom (M:Al.sub.2O.sub.3:P.sub.2O.sub.5:R: Temperature/ Time/ Number Source P Source Agent R Reagent M H.sub.2O) ° C. day MgAPO aluminum phosphoric DIPEA magnesium 0.3:0.9:1:1.8:45 180 5 hydroxide acid nitrate CaAPO boehmite phosphoric TEA calcium 0.1:1:1:3:50 200 4 acid nitrate TiAPO aluminum phosphoric DIPEA titanium 0.15:1:1 1.8:45 160 7 isopropoxide acid sulfate CrAPO aluminum phosphoric TEA chromic 0.1:0.9:1:3:50 160 6 hydroxide acid nitrate MnAPO aluminum phosphoric DIPEA manganese 0.1:0.9:1:1.8:45 160 7 isopropoxide acid acetate FeAPO boehmite phosphoric DIPEA ferric nitrate 0.002:1:1:1.8:45 200 4 acid CoAPO aluminum phosphoric DIPEA cobalt 0.1:0.9:1:1.6:45 160 7 isopropoxide acid nitrate NiAPO boehmite phosphoric TEA nickel 0.2:0.9:1:3:50 180 4 acid nitrate CuAPO boehmite phosphoric DIPEA copper 0.005:1:1:1.8:45 160 6 acid chloride ZnAPO aluminum phosphoric DIPEA zinc acetate 0.1:1:1:1.8:45 200 5 isopropoxide acid GaAPO aluminum phosphoric DIPEA gallium 0.1:0.9:1:1.8:45 160 5 isopropoxide acid nitrate GeAPO aluminum phosphoric DIPEA germanium 0.05:0.9:1:1.6:45 160 7 isopropoxide acid oxide MoAPO boehmite phosphoric DIPEA ammonium 0.2:0.9:1:3:50 180 5 acid molybdate CdAPO aluminum phosphoric DIPEA cadmium 0.1:0.9:1:1.8:45 180 7 hydroxide acid nitrate SrAPO aluminum phosphoric TEA strontium 0.01:1:1:3:50 160 6 nitrate acid nitrate

[0061] Component II′: taking MgSAPO as an example, the raw materials of silica sol, magnesium nitrate, aluminum hydroxide, phosphoric acid, diisopropylethylamine (DIPEA) and deionized water were weighed according to oxide SiO.sub.2:MgO:Al.sub.2O.sub.3:P.sub.2O.sub.5:R:H.sub.2O=0.1:0.3:0.9:1:1.8:45 (molar ratio); and other conditions are the same as the preparation of the component II.

TABLE-US-00004 TABLE 4 Preparation of Heteroatom-Doped Zeolite of AEI Topology and Performance Parameters Zeolite Molar Ratio Hydrothermal Sample Aluminum Template Heteroatom (M:Al.sub.2O.sub.3:P.sub.2O.sub.5: Temperature/ Time/ Number Si Source Source P Source Agent R Reagent M R:H.sub.2O) ° C. day MgSAPO silica sol; aluminum phosphoric DIPEA magnesium 0.3:0.9:1:1.8:45 180 5 Si/P = 0.2 hydroxide acid nitrate CaSAPO boehmite phosphoric TEA calcium 0.1:1:1:3:50 200 4 acid nitrate TiSAPO aluminum phosphoric DIPEA titanium 0.15:1:1:1.8:45 160 7 isopropoxide acid sulfate CrSAPO aluminum phosphoric TEA chromic 0.1:0.9:1:3:50 160 6 hydroxide acid nitrate MnSAPO white aluminum phosphoric DIPEA manganese 0.1:0.9:1:1.8:45 160 7 carbon isopropoxide acid acetate FeSAPO black; boehmite phosphoric DIPEA ferric nitrate 0.002:1:1:1.8:45 200 4 Si/P = 0.01 acid CoSAPO aluminum phosphoric DIPEA cobalt 0.1:0.9:1:1.6:45 160 7 isopropoxide acid nitrate NiSAPO boehmite phosphoric TEA nickel 0.2:0.9:1:3:50 180 4 acid nitrate CuSAPO silica sol; boehmite phosphoric DIPEA copper 0.005:1:1:1.8:45 160 6 Si/P = 0.1 acid chloride ZnSAPO aluminum phosphoric DIPEA zinc acetate 0.1:1:1:1.8:45 200 5 isopropoxide acid GaSAPO aluminum phosphoric DIPEA gallium 0.1:0.9:1:1.8:45 160 5 isopropoxide acid nitrate GeSAPO aluminum phosphoric DIPEA germanium 0.05:0.9:1:1.6:45 160 7 isopropoxide acid oxide MoSAPO white boehmite phosphoric DIPEA ammonium 0.2:0.9:1:3:50 180 5 carbon acid molybdate CdSAPO black; aluminum phosphoric DIPEA cadmium 0.1:0.9:1:1.8:45 180 7 Si/P = 0.6 hydroxide acid nitrate SrSAPO aluminum phosphoric TEA strontium 0.01:1:1:3:50 160 6 nitrate acid nitrate

[0062] (II) Zr—AlPO, Ba—Al PO and Ce—Al PO Zeolites Synthesized by Impregnation Method

[0063] Component II: 100 mL beaker was taken; a zirconium nitrate solution with appropriate concentration was added into the beaker; the solution was stirred and an appropriate amount of AlPO-18 zeolite was added; the solution was stirred at room temperature until the solution was dry; and the solution was dried and roasted at 600° C. for 3 h to obtain Zr—Al PO. Ba—Al PO and Ce—AlPO zeolites were prepared by the above method; and the precursor was replaced with barium nitrate and cerium nitrate.

[0064] Component II′: 100 mL beaker was taken; a zirconium nitrate solution with appropriate concentration was added into the beaker; the solution was stirred and an appropriate amount of SAPO-18 zeolite was added; the solution was stirred at room temperature until the solution was dry; and the solution was dried and roasted at 600° C. for 3 h to obtain Zr-SAPO. Ba-SAPO and Ce-SAPO zeolites were prepared by the above method; and the metal source was replaced with barium nitrate and cerium nitrate.

III. Catalyst Preparation

[0065] The component I and the component II/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 one 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 regulating the interaction between different components.

[0066] 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:

[0067] a) nitrogen and/or inert gas;

[0068] b) mixed gas of hydrogen, nitrogen and/or inert gas, with the volume of hydrogen in the mixed gas being 5-50%;

[0069] c) mixed gas of CO, nitrogen and/or inert gas, with the volume of CO in the mixed gas being 5-20%;

[0070] d) mixed gas of 02, nitrogen and/or inert gas, with the volume of 02 in the mixed gas being 5-20%, wherein the inert gas is one or more than one of helium, argon and neon.

[0071] The mechanical mixing can adopt one or more than one of mechanical agitation, ball milling, rocking bed mixing and mechanical grinding for composition. Specifically:

[0072] Mechanical stirring: mixing the component I and the component II/II′ with a stirring rod in a stirring tank; and regulating the mixing degree of the component I and the component by controlling stirring time (5 min-120 min) and rate (30-300 r/min).

[0073] 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/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.

[0074] Shaking table mixing: premixing the component I and the component II/II′ and placing the components into the container; realizing the mixing of the component I and the component 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).

[0075] Mechanical grinding: premixing the component I and the component 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.

[0076] Specific catalyst preparation and parameter features are shown in Table 5 (component I and component II) and Table 6 (component I and component II′).

TABLE-US-00005 TABLE 5 Preparation of Catalysts (Component I and Component II) and Parameter Features Compounding Mode and Condition Ball Milling Abrasive Mechanical Material, Rocking Polishing Weight Size Bed Pressure ratio of Mechanical Range Oscillation (kg) and Component Agitation and Speed Relative I to Rate Catalyst (r/min) Movement Catalyst Component Component Component (r/min) and Mass and Time Rate Number I II II Time (min) Ratio (min) (r/min) A ZnO#1 MgAPO 0.33 5, 30 B ZnO#2 CaAPO 0.5 100, 250 C ZnO#3 TiAPO 2 5 mm stainless steel ball, 50:1 D MnO CrAPO 1 6 mm stainless steel ball, 60:1 E CeO.sub.2 MnAPO 1 5, 10 F Bi.sub.2O.sub.3 FeAPO 3 60, 100 G In.sub.2O.sub.3 CoAPO 3 5, 30 H Ga.sub.2O.sub.3 NiAPO 1 100, 300 I ZnCr.sub.2O.sub.4 CuAPO 5 6 mm agate ball, 100:1 J ZnAl.sub.2O.sub.4 ZnAPO 1 70, 100 K ZnGa.sub.2O.sub.4 GaAPO 3 15, 200 L ZnIn.sub.2O.sub.4 GeAPO 0.33 20, 300 M MnCr.sub.2O.sub.4 MoAPO 1 100, 300 N MnAl.sub.2O.sub.4 CdAPO 3 6 mm quartz, 100:1 O MnZr.sub.2O.sub.4 SrAPO 0.33 6 mm quartz, 100:1 P MnIn.sub.2O.sub.4 Zr—AlPO 1 10, 100 Q CoAl2O4 Ba—AlPO 1 100, 250 R FeAl.sub.2O.sub.4 Ce—AlPO 3 5 mm stainless steel ball, 50:1 S InAlMnO.sub.7 MgAPO 1 10, 100 T InGaMnO.sub.7 CaAPO 4 50, 60 U dispersed TiAPO 3 10, 100 oxide 1 V dispersed CrAPO 20 5 mm oxide 2 stainless steel ball, 100:1 W dispersed MnAPO 0.5 5, 30 oxide 3 X dispersed FeAPO 1 100, 250 oxide 4 Y dispersed CoAPO 3 5 mm oxide 5 stainless steel ball, 50:1 Z dispersed NiAPO 1.5 6 mm oxide 6 stainless steel ball, 60:1 Z1 dispersed CuAPO 2.5 5, 10 oxide 7 Z2 dispersed ZnAPO 1.5 60, 100 oxide 8 Z3 dispersed GaAPO 2 5, 30 oxide 9 Reference ZnO#4 GeAPO 3 20, 30 example 1 Reference composite MoAPO 2 5 mm example metal stainless 2 ZnCo, the steel ball, molar ratio 50:1 of Zn to Co is 1:1. Reference TiO.sub.2 CdAPO 2 5 mm example stainless 3 steel ball, 50:1

TABLE-US-00006 TABLE 6 Preparation of Catalysts (Component I and Component II′) and Parameter Features Compounding Mode and Condition Ball Milling Abrasive Mechanical Material, Rocking Polishing Weight Size Bed Pressure ratio of Mechanical Range Oscillation (kg) and Component Agitation and Speed Relative I to Rate Catalyst (r/min) Movement Catalyst Component Component Component (r/min) and Mass and Time Rate Number I II′ II′ Time (min) Ratio (min) (r/min) A′ ZnO#1 MgSAPO 0.33 5, 30 B′ ZnO#2 CaSAPO 0.5 100, 250 C′ ZnO#3 TiSAPO 2 5 mm stainless steel ball, 50:1 D′ MnO CrSAPO 1 6 mm stainless steel ball, 60:1 E′ CeO.sub.2 MnSAPO 1 5, 10 F′ Bi.sub.2O.sub.3 FeSAPO 3 60, 100 G′ In.sub.2O.sub.3 CoSAPO 3 5, 30 H′ Ga.sub.2O.sub.3 NiSAPO 1 100, 300 I′ ZnCr.sub.2O.sub.4 CuSAPO 5 6 mm agate ball, 100:1 J′ ZnAl.sub.2O.sub.4 ZnSAPO 1 70, 100 K′ ZnGa.sub.2O.sub.4 GaSAPO 3 15, 200 L′ ZnIn.sub.2O.sub.4 GeSAPO 0.33 20, 300 M′ MnCr.sub.2O.sub.4 MoSAPO 1 100, 300 N′ MnAl.sub.2O.sub.4 CdSAPO 3 6 mm quartz, 100:1 O′ MnZr.sub.2O.sub.4 SrSAPO 0.33 6 mm quartz, 100:1 P′ MnIn.sub.2O.sub.4 Zr—SAPO 1 10, 100 Q′ CoAl2O4 Ba—SAPO 1 100, 250 R′ FeAl.sub.2O.sub.4 Ce—SAPO 3 5 mm stainless steel ball, 50:1 S′ InAlMnO.sub.7 MgSAPO 1 10, 100 T′ InGaMnO.sub.7 CaSAPO 4 50, 60 U′ dispersed TiSAPO 3 10, 100 oxide 1 V′ dispersed CrSAPO 20 5 mm oxide 2 stainless steel ball, 100:1 W′ dispersed MnSAPO 0.5 5, 30 oxide 3 X′ dispersed FeSAPO 1 100, 250 oxide 4 Y′ dispersed CoSAPO 3 5 mm oxide 5 stainless steel ball, 50:1 Z′ dispersed NiSAPO 1.5 6 mm oxide 6 stainless steel ball, 60:1 Z1′ dispersed CuSAPO 2.5 5, 10 oxide 7 Z2′ dispersed ZnSAPO 1.5 60, 100 oxide 8 Z3′ dispersed GaSAPO 2 5, 30 oxide 9 Reference ZnO#4 GeSAPO 3 20, 30 example 1′ Reference composite MoSAPO 2 5 mm example metal stainless 2′ ZnCo, the steel ball, molar ratio 50:1 of Zn to Co is 1:1. Reference TiO.sub.2 CdSAPO 2 5 mm example stainless 3′ steel ball, 50:1

Example of Catalytic Reactions

[0077] 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).

[0078] 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.

[0079] 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 light olefin, 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 generated and the selectivity of the methane is low. Table 7 (component I and component II) and Table 8 (component I and component II′) list specific application and effect data of the catalysts respectively.

TABLE-US-00007 TABLE 7 Specific Application and Effect Data of Catalysts (Component I and Component II) Light Propylene H.sub.2/CO CO Olefin CH.sub.4 and Butylene Temperature Molar Pressure Conversion Selectivity Selectivity Selectivities Embodiments Catalysts GHSV(h.sup.−1) (° C.) Ratio (MPa) Rate % % % % 1 A 5000 415 2.5 4 41.6 71.8 5.7 58.2 2 B 4000 410 1.5 6 31.5 62.7 5.4 42.0 3 C 5000 400 2.5 4 11.3 61.1 6.9 36.7 4 D 7000 420 1 10 37.1 65.3 6.1 54.3 5 E 2000 390 3.5 6 20.2 80.7 4.7 67.3 6 F 2000 410 1.5 3 31.3 64.4 5.5 47.7 7 G 3500 390 3.5 2.5 35.1 73.2 5.4 62.2 8 H 1500 370 2.5 5 19.6 82.1 4.5 64.7 9 I 2500 400 3 3.5 42.0 71.0 2.2 56.5 10 J 2000 410 2.5 8 55.2 73.6 3.4 62.7 11 K 1000 410 2.5 6 20.2 69.1 6.8 50.1 12 L 5000 400 2.5 4 33.0 85.1 2.6 63.1 13 M 10500 520 0.5 1 15.4 72.0 7.6 57.6 14 N 3000 480 0.5 2 31.7 73.4 6.2 60.7 15 O 3000 470 0.5 2 25.4 76.0 5.4 60.8 16 P 3000 450 1 3 30.8 61.9 6.2 40.2 17 Q 3000 450 1.5 3 33.5 65.7 6.8 43.5 18 R 3000 350 3.5 5 33.0 52.2 5.6 40.7 19 S 2000 350 3 7 38.6 55.3 6.9 40.9 20 T 2500 400 1 6 19.0 63.8 5.7 45.7 21 U 4000 400 2 4 10.1 64.2 6.5 41.4 22 V 8000 450 0.5 2 21.1 53.0 6.3 42.6 23 W 2000 410 2 3.5 30.8 78.3 4.9 62.8 24 X 3000 380 3.5 6 31.6 74.4 7.0 56.0 25 Y 5000 390 3 2.5 25.7 69.9 2.5 59.8 26 Z 4000 370 2 10 28.2 83.7 6.7 70.3 27 Z 1 10000 470 1 1.5 17.7 71.1 6.8 57.5 28 Z 2 2000 400 3.5 7 46.8 78.6 4.3 65.7 29 Z 3 3000 380 1.5 2.5 11.3 55.3 6.2 35.1 38 Reference 3000 320 0.5 1 1.1 26.0 37.2 11.1 example 1 39 Reference 4000 450 3 3 24.4 33.4 25.3 13.2 example 2 40 Reference 2000 350 2.5 3 0.1 18.4 67.2 6.6 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 45 Reference 5000 415 2.5 4 8.4 59.0 20.6 40.2 example 8 46 Reference 5000 415 2.5 4 9.4 55.4 22.6 37.1 example 9 47 Reference 4000 410 1.5 6 17.3 57.7 21.4 38.3 example 10

[0080] In reference example 1, the catalyst component I is ZnO #4, and component II is GeAPO.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] The zeolite in the catalyst adopted in reference example 8 is self-synthetic AlPO-18. Other parameters and the mixing process are the same as those of catalyst A. The conversion rate and selectivity of the reaction in the reference example 8 are very poor, which are far lower than the reaction performance of catalyst A under the same conditions. This indicates that the zeolite doped with the heteroatoms can effectively improve the reaction activity and selectivity.

[0088] The zeolite in the catalyst adopted in reference example 9 is AlPO-18 after Mg(NO.sub.3).sub.2 ion exchange. Other parameters and the mixing process are the same as those of catalyst A.

[0089] The zeolite in the catalyst adopted in reference example 10 is AlPO-34 after Ca(NO.sub.3).sub.2 ion exchange. Other parameters and the mixing process are the same as those of catalyst B.

[0090] The reaction results of reference example 9 and reference example 10 show that the reaction performance of ion-exchanged AlPO-18 and AlPO-34 samples as catalyst component II has obvious gap from the heteroatom-doped zeolite of the present invention; and the doping of the heteroatoms in the AlPO zeolite skeleton is very important for the reaction activity and selective modulation.

TABLE-US-00008 TABLE 8 Specific Application and Effect Data of Catalysts (Component I and Component II′) Light Propylene H.sub.2/CO CO Olefin CH.sub.4 and Butylene Temperature Molar Pressure Conversion Selectivity Selectivity Selectivities Embodiments Catalysts GHSV(h.sup.−1) (° C.) Ratio (MPa) Rate % % % % 1 A′ 5000 400 2.5 5 38.7 78.6 4.7 62.2 2 B′ 4000 410 1.5 9 30.5 60.2 6.4 44.0 3 C′ 5000 400 2.5 4 21.3 65.1 6.8 50.7 4 D′ 7000 420 1 10 51.1 66.4 6.1 54.8 5 E′ 2000 390 3.5 6 27.3 81.5 4.7 72.4 6 F′ 2000 410 1.5 3 34.1 61.1 5.5 49.8 7 G′ 3500 390 3.5 2.5 38.2 71.3 5.4 60.7 8 H′ 1500 370 2.5 5 24.6 75.4 6.5 60.1 9 I′ 2500 400 3 3.5 45.2 69.3 4.2 56.0 10 J′ 2000 410 2.5 8 57.5 73.1 6.4 61.4 11 K′ 1000 410 2.5 6 30.7 65.2 6.8 50.6 12 L′ 5000 400 2.5 4 42.1 76.3 3.6 64.5 13 M′ 10500 520 0.5 1 15.4 51.1 2.6 43.5 14 N′ 3000 480 0.5 2 34.6 63.4 4.2 50.2 15 O′ 3000 470 0.5 2 32.4 66.0 4.8 56.7 16 P′ 3000 450 1 3 30.8 65.4 5.2 52.2 17 Q′ 3000 450 1.5 3 38.5 61.2 6.8 48.3 18 R′ 3000 350 3.5 5 37.3 50.1 5.6 39.7 19 S′ 2000 350 3 7 41.6 51.3 5.9 40.9 20 T′ 2500 400 1 6 28.1 69.8 5.7 45.7 21 U′ 4000 400 2 4 30.1 66.2 6.5 54.4 22 V′ 8000 450 0.5 2 18.1 63.0 3.3 52.1 23 W′ 2000 410 2 3.5 32.8 75.3 4.9 64.4 24 X′ 3000 380 3.5 6 38.6 72.4 5.1 54.2 25 Y′ 5000 390 3 2.5 28.1 65.4 3.5 57.2 26 Z′ 4000 370 2 10 31.2 71.7 6.1 55.3 27 Z 1′ 10000 470 1 1.5 21.7 69.8 3.8 51.7 28 Z 2′ 2000 400 3.5 7 51.8 72.3 6.1 60.8 29 Z 3′ 3000 380 1.5 2.5 21.3 57.3 6.2 39.8 38 Reference 3000 320 0.5 1 1.3 28.5 32.1 16.6 example 1′ 39 Reference 4000 450 3 3 27.5 30.2 21.4 15.7 example 2′ 40 Reference 2000 350 2.5 3 0.2 18.3 64.4 9.8 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′ 45 Reference 5000 400 2.5 5 40.6 68.8 5.7 54.2 example 8′ 46 Reference 4000 410 1.5 9 30.5 52.2 10.2 34.0 example 9′ 47 Reference 5000 400 2.5 4 21.3 55.1 15.8 35.7 example 10′

[0091] In reference example 1′, the catalyst component I is ZnO #4, and component II′ is GeSAPO.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] The zeolite in the catalyst adopted in reference example 8′ is self-synthetic SAPO-18. Other parameters and the mixing process are the same as those of catalyst A′. Catalyst A doped with Mg on the basis of the reaction of reference example 8 having higher conversion rate and poor selectivity can effectively improve the selectivity for light olefin.

[0099] The zeolite in the catalyst adopted in reference example 9′ is SAPO-18, after Mg(NO.sub.3).sub.2 ion exchange. Other parameters and the mixing process are the same as those of catalyst A′.

[0100] The zeolite in the catalyst adopted in reference example 10′ is SAPO-34 after Ca(NO.sub.3).sub.2 ion exchange. Other parameters and the mixing process are the same as those of catalyst B′.

[0101] The reaction results of reference example 9′ and reference example 10′ show that the reaction performance of ion-exchanged SAPO-18 and SAPO-34 samples as catalyst component II′ has obvious gap from the heteroatom-doped zeolite of the present invention; and the conversion rate and the selectivity are obviously reduced. The doping of the heteroatoms in the SAPO zeolite skeleton is very important for the reaction activity and selective modulation.

[0102] 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%.

[0103] It is observed from the above table that, the structure of the zeolite including the topologies, acid strength and acid amount of CHA&AEI, doping amount of heteroatoms and doping in the skeleton, 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.