CATALYST CONTAINING LF-TYPE B ACID AND METHOD FOR PREPARING ETHYLENE USING DIRECT CONVERSION OF SYNGAS

Abstract

A catalyst containing LF-type B acid preparing ethylene using direct conversion of syngas is a composite catalyst and formed by compounding component A and component B in a mechanical mixing mode. The active ingredient of the component A is a metal oxide; the component B is a zeolite of MOR topology; and a weight ratio of the active ingredients in the component A to the component B is 0.1-20. The reaction process has an extremely high product yield and selectivity, with the selectivity for light olefin reaching 80-90%, wherein ethylene has high space time yield and can reach selectivity of 75-80%. Meanwhile, the selectivity for a methane side product is extremely low (<15%).

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; 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 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.sup.(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 MOR zeolite in the component B comprises LF-type B acid; and the content range of the LF-type B acid is 0.01 mmol/g-0.6 mmol/g, preferably 0.1-0.6 mmol/g and more preferably 0.3-0.6 mmol/g.

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

3. The catalyst according to claim 1, wherein a dispersing agent is also added to the component I; the metal oxide is dispersed in the dispersing agent; and 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.

4. The catalyst according to claim 1, wherein, in the component I, the content of the dispersing agent is 0.05-90 wt %.

5. The catalyst according to claim 1, wherein a skeleton element composition of the zeolite of the MOR topology is at least one of SiAlO, GaSiO, TiSiO, TiAlSiO, CaAlO, and CaSiAlO.

6. A method for preparing light olefin comprising converting syngas to the light olefin in the presence of the catalyst of claim 1.

7. The method according to claim 6, wherein the converting is carried out under a pressure of 0.5-10 MPa, a reaction temperature of 300-600 C., a space velocity of 300-10000 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.

8. The method according to claim 6, wherein the light olefin comprises C.sub.2-4 olefin, and the method achieves a selectivity for ethylene of 75-80%, and a selectivity for a methane side product of lower than 15%.

9. 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, 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.aAl.sub.bMn.sub.(1-a-b)O.sub.x, and In.sub.aGa.sub.bMn.sub.(1-a-bO.sub.x is 50-150 m.sup.2/g.

10. The catalyst according to claim 2 wherein the weight ratio of the active ingredients in the component I to the component II is 0.3-8.

11. The catalyst according to claim 4, wherein in the component I, the content of the dispersing agent is 0.05-25 wt %.

12. The method according to claim 7, wherein the pressure is 0.5-10 MPa, the reaction temperature is 300 C.-450 C., the-space velocity is 500-9000 and the ratio of H.sub.2/CO is 0.3-2.5.

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

Description

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0027] 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.

[0028] 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:

[0029] I. Preparation of Component I of Catalyst

[0030] (I) ZnO material with high specific surface area was synthesized through a precipitation method:

[0031] (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;

[0032] (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.

[0033] 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.

[0034] 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 Roasting Specific Sample Roasting Temperature/ Roasting Surface Number Time/h C. Atmosphere Area 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

[0035] (II) MnO Material with High Specific Surface Area was Synthesized Through a Coprecipitation Method:

[0036] 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.

[0037] (III) CeO.sub.2 Material with High Specific Surface Area was Synthesized Through a Coprecipitation Method:

[0038] 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.

[0039] (IV) Ga.sub.2O.sub.3 Material with High Specific Surface Area was Synthesized Through a Coprecipitation Method:

[0040] 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.

[0041] (V) Bi.sub.2O.sub.3 Material with High Specific Surface Area was Synthesized 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 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.

[0043] (VI) In.sub.2O.sub.3 Material with High Specific Surface Area was Synthesized Through a 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 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.

[0045] (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, 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, FeaAl.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

[0046] 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 Specific Elements and Final Molar Aging Aging Roasting Surface Concentration of One Temperature Time Temperature Roasting Area Metal Oxide Metal in Water (mmol/L) C. h C. Time h m.sup.2/g ZnCr.sub.2O.sub.4 ZnCr = 1:2, and Zn is 120 24 500 2 126 50 mM ZnAl.sub.2O.sub.4 ZnAl = 1:2, and Zn is 130 20 400 4 137 50 mM ZnGa.sub.2O.sub.4 ZnGa = 1:2, and Zn is 130 20 400 4 110 50 mM ZnIn.sub.2O.sub.4 ZnIn = 1:2, and Zn is 130 20 400 4 87 50 mM 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 145 16 400 2 15 is 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 MnIn = 1:2, and Mn is 150 12 500 1 67 50 mM CoAl.sub.2O.sub.4 CoAl = 1:2, and Co is 145 16 400 2 22 50 mM FeAl.sub.2O.sub.4 FeAl = 1:2, and Fe is 145 16 400 2 30 50 mM InAl.sub.3MnO.sub.7 In:Al: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 145 16 400 2 67 is 50 mM

[0047] (VIII) Metal Oxide Dispersed in Dispersing Agent Cr.sub.2O.sub.3, Al.sub.2O.sub.3 or ZrO.sub.2

[0048] 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 (the specific surface area is about 5 m.sup.2/g), 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.

[0049] 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.

[0050] 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.

[0051] II. Preparation of Component II (Zeolite of MOR Topology)

[0052] 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 pockets are communicated on the side edges of the 12-ring porous channels.

[0053] The determination of the content of the LF-type B acid may be but not limited to: firstly, a solid nuclear magnetic H spectrum or NH.sub.3-TPD is used to quantitatively measure the content of all B acids in MOR; then three peaks of LF, HF and TF are fitted through vacuum in-situ infrared OH vibration peak signals; the percentage of LF in all B acids is calculated according to the relative proportion of peak area; and then the content of the LF-type B acid is calculated according to the product of the content of all B acids in MOR and the percentage of LF in all B acids. The fitting and attribution of the three acids are based on the literature N. Cherkasov et al./Vibrational Spectroscopy 83(2016)170-179.

[0054] The component II zeolite of the present invention may be a purchased commercial product (a zeolite which conforms to the content range 0.01 mmol/g-0.6 mmol/g of the LF-type B acid is selected), such as commercial mordenite from Nankai University Catalyst Plant; or commercial MOR-SAR=15 from Shentan Catalyst Company;

[0055] or a prepared zeolite, taking hydrothermal synthesis as an example herein.

[0056] 1) The specific preparation process is: 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(H2P)/n(SiO.sub.2)=26; then, silica sol was added and stirred for 1 h to obtain homogeneous phase initial gel; then, the mixture was transferred into a synthesis autoclave, was statically crystallized at 180 C. for 24 h, and then was quenched, washed and dried to obtain a mordenite sample, labeled as Na-MOR.

[0057] Na-MOR was taken, mixed with 1 mol/L ammonium chloride solution, stirred at 90 C. for 3 h, washed, dried for two times in succession, and roasted at 450 C. for 6 h to obtain H-mordenite.

[0058] The skeleton element composition of the zeolite of the MOR topology prepared by the above process may be one of SiAlO, GaSiO, GaSiAlO, TiSiO, TiAlSiO, CaAlO and CaSiAlO. O element of part of the skeleton is connected with H, and corresponding products are successively defined as MOR1-8.

TABLE-US-00003 TABLE 3 Preparation of Zeolite of MOR Topology and Performance Parameters Si and Hydrothermal LF Acid Sample Ca Al, Ga and Ti Temperature Time Amount Number Sources Sources Molar Ratio ( C.) (Day) mmol/g MOR1 TEOS sodium n(SiO.sub.2)/n(Al.sub.2O.sub.3) = 16, 170 1.3 0.48 metaaluminate n(Na.sub.2O)/n(SiO.sub.2) = 0.3 n(H.sub.2O)/n(SiO.sub.2) = 27 MOR2 silica Al(OH)3 n(SiO.sub.2 + CaO)/n(Al.sub.2O.sub.3) = 8, 183 0.9 0.35 sol n(SiO.sub.2)/n(CaO) = 43, Ca(OH) n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 26 MOR3 TEOS AlOOH n(SiO.sub.2)/n(Al.sub.2O.sub.3 + Ga.sub.2O.sub.3) = 22, 181 1.3 0.30 gallium nitrate n(Ga.sub.2O.sub.3)/n(AhO.sub.3) = 7, n(Na.sub.2O)/n(SiO.sub.2) = 0.3 n(H.sub.2O)/n(SiO.sub.2) = 26 MOR4 silica titanium sol n(SiO.sub.2)/n(TiO.sub.2) = 70, 188 0.8 0.25 sol n(Na.sub.2O)/n(SiO.sub.2) = 0.3 n(H.sub.2O)/n(SiO.sub.2) = 26 MOR5 silica aluminum n(SiO.sub.2)/n(Al.sub.2O.sub.3) = 6, 188 0.7 0.22 sol sulfate n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 27 MOR6 silica aluminum n(SiO.sub.2)/n(Al.sub.2O.sub.3) = 4, 182 1.1 0.15 sol 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) = 19, 173 1.6 0.08 sulfate n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 28 MOR8 silica titanium sol n(SiO.sub.2)/n(Al.sub.2O.sub.3 + TiO.sub.2) = 25, 182 0.9 0.02 sol AlOOH n(TiO.sub.2)/n(Al.sub.2O.sub.3) = 1, n(Na.sub.2O)/n(SiO.sub.2) = 0.2 n(H.sub.2O)/n(SiO.sub.2) = 25 Commercial mordenite from Nankai University Catalyst Plant 0.13 Commercial MOR-SAR = 15 from Shentan Catalyst Company 0.27

III. Catalyst Preparation

[0059] 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.

[0060] 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:

[0061] a) nitrogen and/or inert gas;

[0062] b) mixed gas of hydrogen, nitrogen and/or inert gas, with the volume of hydrogen in the mixed gas being 5-50%;

[0063] c) mixed gas of CO, nitrogen and/or inert gas, with the volume of CO in the mixed gas being 5-20%;

[0064] d) mixed gas of 02, 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.

[0065] The mechanical mixing can adopt one or more than one of mechanical agitation, ball milling, rocking bed mixing and mechanical grinding for composition. Specifically:

[0066] 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).

[0067] 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.

[0068] 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).

[0069] 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.

[0070] Specific catalyst preparation and parameter features are shown in Table 4.

TABLE-US-00004 TABLE 4 Preparation of Catalysts and Parameter Features Compounding Mode and Condition Ball Milling Abrasive Mechanical Mechanical Material, Rocking Polishing Agitation Size Bed Pressure Rate Range and Oscillation (kg) and Weight (r/min) Catalyst Speed Relative Catalyst Ratio of I and Time Mass (r/min) and Movement Number Component I Component II to II (min) Ratio Time (min) Rate (r/min) A ZnO#1 MOR1 0.33 5, 30 B ZnO#2 MOR2 0.5 100, 250 C ZnO#3 MOR3 2 5 mm stainless steel ball, 50:1 D MnO MOR4 1 6 mm stainless steel ball, 60:1 E CeO.sub.2 MOR5 1 5, 10 F Bi.sub.2O.sub.3 MOR6 3 60, 100 G In.sub.2O.sub.3 MOR7 3 5, 30 H Ga.sub.2O.sub.3 MOR8 1 100, 300 I ZnCr.sub.2O.sub.4 MOR1 5 6 mm agate ball, 100:1 J ZnAl.sub.2O.sub.4 MOR2 1 70, 100 K ZnGa.sub.2O.sub.4 MOR3 3 15, 200 L ZnIn.sub.2O.sub.4 MOR4 0.33 20, 300 M MnCr.sub.2O.sub.4 MOR5 1 100, 300 N MnAl.sub.2O.sub.4 MOR6 3 6 mm quartz, 100:1 O MnZr.sub.2O.sub.4 MOR7 0.33 6 mm quartz, 100:1 p MnIn.sub.2O.sub.4 MOR8 1 10, 100 Q CoAl.sub.2O.sub.4 MOR1 1 5, 10 R FeAl.sub.2O.sub.4 MOR2 3 60, 100 S InAl.sub.3MnO.sub.7 MOR3 3 5, 30 T InGa.sub.2MnO.sub.7 MOR4 1 100, 300 U dispersed oxide MOR5 0.33 6 mm 1 quartz, 100:1 V dispersed oxide MOR6 1 100, 250 2 W dispersed oxide MOR7 3 5 mm 3 stainless steel ball, 50:1 X dispersed oxide MOR8 1 10, 100 4 Y dispersed oxide MOR1 4 50, 60 5 Z dispersed oxide MOR2 3 10, 100 6 Z1 dispersed oxide MOR3 20 5 mm 7 stainless steel ball, 100:1 Z2 dispersed oxide MORI 16 100, 200 8 Z3 dispersed oxide MORI 0.1 20, 100 9 Z4 dispersed oxide Commercial 0.33 6 mm 1 mordenite from quartz, Nankai 100:1 University Catalyst Plant Z5 dispersed oxide Commercial 1 100, 250 2 MOR-SAR = 15 from Shentan Catalyst Company Reference ZnO#4 MOR1 3 20, 30 example 1 Reference composite MOR1 0.33 5, 30 example 2 metal ZnCo, the molar ratio of Zn to Co is 1:1. Reference TiO.sub.2 MOR1 0.33 5, 30 example 3

Example of Catalytic Reactions

[0071] 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).

[0072] 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 500-10000 ml/g/h. On-line chromatography is used to detect and analyze the product.

[0073] The reaction performance can be changed by changing the temperature, pressure and space velocity. The selectivity of the light olefin (one or more than one of ethylene, propylene and butylene) in the product can reach 80-90%, and the conversion rate of the raw material is 10-60%. Because the hydrogenation activity of the surface of the metal composite of the catalysts is not high, mass production of methane is avoided. The selectivity for the methane is low, wherein the selectivity for the ethylene is 75-80%.

TABLE-US-00005 TABLE 5 Application and Effect of Catalysts Ethylene Space Time Yield H.sub.2/CO mmol Light Olefin CH.sub.4 Ethylene GHSV Temperature Molar Pressure Olefin/h .Math. g Selectivity Selectivity Selectivity Embodiment Catalyst (h-.sup.1) ( C.) Ratio (MPa) Catalyst % % % 1 A 3500 400 2 3.5 0.70 87 8 76 2 B 3000 400 1.5 9 0.52 87 7 78 3 C 1000 370 2 5.5 0.31 87 7 77 4 D 5000 450 1.5 3 0.38 84 9 76 5 E 3000 430 3 1.5 0.66 83 11 75 6 F 2000 380 0.5 7 0.68 84 13 75 7 G 3000 360 2 5.5 0.14 81 14 75 8 H 1500 380 2.5 5 0.10 80 14 75 9 I 2300 350 1 3 1.16 88 6 78 10 J 3000 410 2.5 8 0.91 90 5 80 11 K 5000 400 2 4 0.86 90 5 80 12 L 2500 120 1 4 0.56 86 7 75 13 M 8000 470 0.5 1 0.28 80 9 75 14 N 4000 410 3 3 0.12 81 10 75 15 O 5000 370 2 4 0.22 83 14 75 16 P 3000 370 1.5 6.8 0.21 83 15 75 17 Q 3500 350 1 5 0.46 85 9 78 18 R 3000 450 0.5 5.8 0.53 83 8 77 19 S 2000 430 1 7 0.82 89 7 80 20 T 7000 410 2.5 2 0.54 83 8 76 21 U 2500 370 1.5 7 0.62 84 8 77 22 V 3000 350 2 5 0.48 82 11 75 23 W 2000 350 1 4 0.22 83 13 75 24 X 2500 410 1.5 6 0.06 81 15 75 25 Y 4000 400 2 4 0.80 89 9 77 26 Z 3500 410 3.5 3 0.76 88 8 77 27 Z1 8000 450 1.5 1 0.22 80 14 75 28 Z2 4000 410 3 3.5 0.21 81 12 75 29 Z3 2500 400 0.5 10 0.10 81 7 75 30 Z4 4000 360 1 4 0.23 80 14 75 31 Z5 5000 375 1 3 0.35 80 13 75 32 Reference 1000 300 0.5 1 0.01 35 55 20 example 1 33 Reference 4000 450 3 3 0.66 33 35 11 example 2 34 Reference 2000 350 2.5 3 0.01 25 70 11 example 3 35 Reference 3000 400 1 4 0.08 55 7 19 example 4 36 Reference 3000 400 2 3.5 0.03 34 11 11 example 5 37 Reference 2500 400 2 3.5 0.05 45 19 30 example 6 38 Reference 2500 400 2 3.5 0.02 25 23 7 example 7 39 Reference 3000 450 2.5 4 <0.01 1.5 50 0.8 example 8 40 Reference 2200 450 3 2 <0.01 example 9 41 Reference 3000 420 3 2 <0.2 37 38 14 example 10

[0074] The catalyst adopted in reference example 4 replaces the zeolite of the catalyst A with the commercial SAPO-34 purchased from Nankai University Catalyst Factory.

[0075] The catalyst adopted in reference example 5 replaces the zeolite of the catalyst A with commercial ZSM-5 of full micropore structure with Si/Al=30, purchased from Nankai University Catalyst Factory.

[0076] Reaction results of reference examples 4 and 5 show that, the MOR topology is crucial to the selective modulation of the products; SAPO.sub.34 has an orifice size of 3.8A, and is suitable for C2-C4 hydrocarbons, but more C3 products are produced and the selectivity for ethylene is not high. The ZSM5 has larger orifice size of 5.6A, and the products are mainly C4 hydrocarbons and even hydrocarbons with longer carbon chains.

[0077] The MOR has large orifice size of 6.57.0A, but also contains a side pocket of 8-ring orifice. The depth of the pocket is shallower than that of the SAPO34 pocket. Thus, ethylene with two carbon atoms is mainly produced, and has advantageous features not found in other structural zeolites. The acid at the LF site is mainly located in the 8-ring pocket, and thus is crucial for the production of the ethylene.

[0078] The catalyst used in reference example 6 is basically consistent with the catalyst C sample, and the differences are that the sodium nitrate is used for ion exchange of the MOR3 zeolite; the LF-type B acid is partially replaced with Na; the content of the LF acid is measured as 0.005 mmol/g through solid nuclear magnetic resonance hydrogen spectroscopy and infrared quantitative measurement, while the retained contents of HF and TF acids are 0.6 mmol/g and 0.3 mmol/g respectively.

[0079] The determination of the content of the LF-type B acid may be but not limited to: firstly, a solid nuclear magnetic H spectrum or NH.sub.3-TPD is used to quantitatively measure the content of all B acids in MOR; then three peaks of LF, HF and TF are fitted through vacuum in-situ infrared OH vibration peak signals; the percentage of LF in all B acids is calculated according to the relative proportion of peak area; and then the content of the LF-type B acid is calculated according to the product of the content of all B acids in MOR and the percentage of LF in all B acids. The fitting and attribution of the three acids are based on the literature N. Cherkasov et al./Vibrational Spectroscopy 83(2016)170-179.

[0080] The catalyst used in reference example 7 is basically consistent with the catalyst C sample, and the differences are that the sodium nitrate is used for ion exchange of the MOR3 zeolite; the LF-type B acid is replaced with Na; the content of the LF acid is measured as 0.001 mmol/g through solid nuclear magnetic resonance hydrogen spectroscopy and infrared quantitative measurement, while the retained contents of HF and TF acids are 0.5 mmol/g and 0.3 mmol/g respectively. The reaction results show that the LF acid in MOR is critical to the space time yield of the ethylene. When the acid of LF is lower than the scope of the claims, the ethylene yield drops sharply. After the acid of LF is almost completely replaced, the ethylene yield also correspondingly drops to be extremely low, indicating the importance of the LF acid for the direct preparation of the ethylene by using syngas.

[0081] The catalyst adopted in reference example 8 is a sample containing only component I ZnO #1 without the component II, 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.

[0082] The catalyst adopted in reference example 9 is a sample containing only the zeolite of component II without the component I, and the catalytic reaction almost has no activity.

[0083] Reference examples 8 and 9 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.

[0084] Embodiments Z4 and Z5 are commercially available zeolites. Because the acid content meets the requirements of the present invention, the zeolites exhibit excellent catalytic performance.

[0085] The catalyst adopted in reference example 10 replaces the zeolite of the catalyst A with the commercial MOR-SAR=5 purchased from Shentan Catalyst Company. Because the acid amount of LF in the zeolite is less than 0.01 mmol/g and a gas-phase intermediate generated on the metal oxide cannot be converted well, a large amount of methane is produced and the requirements of the present invention cannot be satisfied. Therefore, it is very important to select a proper commercial zeolite.

[0086] It is observed from the above table that, the structure of the zeolite including the MOR topology, and the matching between the metal oxide and the zeolite are crucial and directly affect the selectivity of the light olefin and the ethylene.