CN111346672A - Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve - Google Patents

Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve Download PDF

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CN111346672A
CN111346672A CN201811575056.4A CN201811575056A CN111346672A CN 111346672 A CN111346672 A CN 111346672A CN 201811575056 A CN201811575056 A CN 201811575056A CN 111346672 A CN111346672 A CN 111346672A
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molecular sieve
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synthesis gas
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焦峰
李�根
潘秀莲
包信和
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Dalian Institute of Chemical Physics of CAS
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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    • C07C2529/00—Catalysts comprising molecular sieves
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    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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Abstract

The invention relates to a catalyst containing a heteroatom-doped molecular sieve and a method for preparing low-carbon olefin by directly converting synthesis gas, wherein the catalyst is a composite catalyst, a component I and a component II are compounded together in a mechanical mixing mode, the active ingredient of the component I is a metal oxide, the component II is the heteroatom-doped molecular sieve, the topological structure of the molecular sieve is CHA or AEI, framework atoms comprise Al, P, O and Si, and the heteroatoms can be one or more of divalent metals such as Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo, Cd, Ba, Ce, trivalent Ti, Ga and tetravalent Ge; the weight ratio of the active component I to the component II in the component I is in the range of 0.1-20 times. The reaction process has high selectivity of low-carbon olefin, the sum of the selectivity of the low-carbon olefin including ethylene, propylene and butylene can reach 50-90%, and the selectivity of the byproduct methane is lower than 7%, so that the method has a good application prospect.

Description

Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve
Technical Field
The invention belongs to the field of low-carbon olefin preparation by using synthesis gas, and particularly relates to a method for preparing low-carbon olefin by catalyzing synthesis gas through a heteroatom-doped molecular sieve.
Background
The lower olefin is an olefin having 4 or less carbon atoms. The low-carbon olefin represented by ethylene and propylene is a very important basic organic chemical raw material, and the market of the low-carbon olefin is short in supply and demand for a long time along with the rapid growth of the economy of China. At present, the production of low-carbon olefin mainly adopts a petrochemical route of light hydrocarbon (ethane, naphtha and light diesel oil) cracking, and due to the gradual shortage of global petroleum resources and the long-term high-order running of the price of crude oil, the development of the tubular cracking furnace process which only depends on the light hydrocarbon as the raw material in the low-carbon olefin industry encounters larger and larger raw material problems, and the production process and the raw material of the low-carbon olefin need to be diversified. The process for preparing olefin by selecting synthesis gas can broaden the source of raw materials, and provides an alternative scheme for the steam cracking technology based on high-cost raw materials such as naphtha by using crude oil, natural gas, coal and renewable materials as raw materials to produce synthesis gas. The one-step method for directly preparing the low-carbon olefin from the synthesis gas is a process for directly preparing the low-carbon olefin with the carbon atom number less than or equal to 4 by the Fischer-Tropsch synthesis reaction of carbon monoxide and hydrogen under the action of the catalyst, and the process does not need to further prepare the olefin from the synthesis gas through methanol or dimethyl ether like an indirect process, thereby simplifying the process flow and greatly reducing the investment.
The direct preparation of low-carbon olefin from synthesis gas through Fischer-Tropsch synthesis becomes one of the research hotspots for developing Fischer-Tropsch synthesis catalysts. In patent CN1083415A published by institute of chemical and physical sciences in the chinese academy of sciences, an iron-manganese catalyst system supported by an alkali metal oxide of group IIA such as MgO or a high-silicon zeolite molecular sieve (or a phospho-aluminum zeolite) is used, and strong base K or Cs ions are used as an auxiliary agent, so that high activity (90% of CO conversion) and high selectivity (66% of low-carbon olefin selectivity) can be obtained at a reaction temperature of 300-400 ℃ under a reaction pressure of 1.0-5.0 MPa for preparing low-carbon olefin from synthesis gas. In patent ZL03109585.2 filed by Beijing university of chemical industry, a vacuum impregnation method is adopted to prepare a Fe/activated carbon catalyst taking manganese, copper, zinc, silicon, potassium and the like as additives for the reaction of preparing low-carbon olefin from synthesis gas, and under the condition of no circulation of raw material gas, the conversion rate of CO is 96 percent, and the selectivity of the low-carbon olefin in hydrocarbon is 68 percent. Recently, a Netherlands university of Utrecht de Jong teaches a team that Fe supported by inert carriers such as SiC, carbon nanofibers and the like and Fe catalysts modified by auxiliaries such as Na, S and the like are adopted to achieve good progress and obtain 61% of low-carbon olefin selectivity, but when the conversion rate is increased, the selectivity is reduced. In the process of directly preparing olefin from synthesis gas, because the raw materials CO and H2 are gaseous, and the boiling point of ethylene in a target product is low, cryogenic separation is generally needed, if olefin containing three carbon atoms and four carbon atoms, namely propylene and butene C3-C4 olefin products, can be obtained with high selectivity, cryogenic separation is not needed, the energy consumption and cost of separation are greatly reduced, and the method has great application value. In the above reports, the catalyst adopts metallic iron or iron carbide as an active component, the reaction follows a chain growth reaction mechanism on the metal surface, the selectivity of the product low-carbon olefin is low, and the selectivity of the C3-C4 olefin is lower.
ZnCr was reported recently by the institute of chemical and physical university of Chinese academy of sciences2O4The oxide and multi-stage pore SAPO-34 molecular sieve composite bifunctional catalyst (Jiao et al, Science 351(2016)1065-1068) realizes the selectivity of low-carbon olefin of 80 percent when the CO conversion rate is 17 percent, wherein the selectivity of low-carbon alkane is 14 percent, the ratio of olefin to alkane (alkene ratio) reaches 5.7, when the conversion rate is increased to 35 percent, the selectivity of olefin is 69 percent, the selectivity of alkane is 20 percent, the alkene ratio is reduced to 3.5, and the selectivity of propylene and butene is 40-50 percent.
Disclosure of Invention
Aiming at the problems, the invention provides a catalyst and a method for preparing low-carbon olefin by directly converting synthesis gas.
The technical scheme of the invention is as follows:
the invention provides a catalyst, which comprises a component I and a component II, wherein the component I and the component II are respectively prepared and then mixed to obtain the catalyst; the active component of the component I is metal oxide, and the component II is a doped heteroatom molecular sieve;
the metal oxide is MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxOne or more than two of them; the value range of x is 0.7-3.7, and the value range of a is 0-1; the value range of a + b is 0-1;
the molecular sieve is a CHA or AEI topological structure molecular sieve, the framework atoms comprise Al, P, O and Si, and the hetero atoms can be one or more of divalent metals such as Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo, Cd, Ba and Ce, trivalent Ti, Ga and tetravalent Ge; the molecular sieve doped with the heteroatoms is formed by doping the heteroatoms in the molecular sieve framework to replace Al, Si or P in the molecular sieve framework, usually, divalent metals and trivalent metals replace the position of Al in the framework, and metals with valences of four or more replace the position of Si or P.
Based on the above technical scheme, preferably, the MnOx、ZnOx、CeOx、GaOx、BiOx、InOxHas a specific surface area of 1 to 100m2(ii)/g; the preferred specific surface area is 50 to 100m2/g；
The MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxHas a specific surface area of 5 to 150m2A preferred specific surface area is from 50 to 150m2/g。
Based on the technical scheme, preferably, the ratio of the sum of the molar weights of the heteroatoms in the heteroatom-doped molecular sieve to the molar weight of P is 0.001-0.6; the molar weight ratio of Si atoms to P is 0.01-0.6.
Based on the technical scheme, the weight ratio of the active ingredients in the component I to the component II is preferably 0.1-20, and preferably 0.3-5.
Based on the technical scheme, preferably, a dispersant can be further added into the component I, and the metal oxide is dispersed in the dispersant; the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more of activated carbon, graphene and carbon nanotubes. In the component I, the content of the dispersant is 0.05 to 90 weight percent, and the balance is metal oxide.
Based on the technical scheme, preferably, the heteroatom-doped molecular sieve 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) preparing a sol precursor: in the process of preparing the sol precursor, dissolving an aluminum source, a phosphorus source and a silicon source in a certain proportion in water, uniformly stirring, adding the precursor containing the heteroatom and a template agent, and stirring for 0.5-12 h; (2) hydrothermal crystallization: carrying out reaction crystallization on the sol precursor obtained in the step (1) at the temperature of 160-200 ℃ for 4-7 days; (3) separation and washing: centrifuging and washing a product after the crystallization reaction; (4) drying and roasting; roasting the product obtained in the step (3) at the temperature of 550-600 ℃ for 3-6 h; the ratio of the heteroatom precursor heteroatom to the phosphorus source is 0-0.6; the post-treatment method comprises the following steps: preparing a solution of a heteroatom precursor, soaking the SAPO-18 or SAPO-34 molecular sieve in the precursor solution, drying, and finally roasting at 550-600 ℃ for 3-6 h. And loading by an impregnation method to obtain a heteroatom precursor, and embedding the heteroatom into the framework in a roasting mode. The SAPO-18 or SAPO-34 can be a commercially available sample or a sample synthesized by a method reported in the literature.
Based on the above technical scheme, preferably, the aluminum source includes but is not limited to boehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum isopropoxide; the silicon source includes but is not limited to silica sol, TEOS, white carbon black, quartz sand, silicate; the heteroatom precursors include, but are not limited to, metal nitrates, sulfates, acetates, halides, oxides; the template agent is Triethylamine (TEA), Diisopropylethylamine (DIPEA) and the like.
The two prepared molecular sieves doped with heteroatoms are obviously different from the molecular sieves doped with heteroatoms in ion exchange, the heteroatoms of the molecular sieves obtained by the conventional ion exchange replace H on Si-OH-Al and are positioned outside a molecular sieve framework, the heteroatoms of the molecular sieves doped with heteroatoms obtained by the method are embedded into the molecular sieve framework, and the catalyst structure and the reaction performance are obviously different from those of an ion exchange sample.
On the other hand, the invention provides a method for preparing low-carbon olefin by catalyzing synthesis gas with high selectivity, which takes the synthesis gas as a reaction raw material to carry out conversion reaction on a fixed bed or a moving bed to prepare the low-carbon olefin, wherein the catalyst adopted by the method is the catalyst in claim 1.
Based on the technical scheme, the pressure of the synthesis gas is preferably 0.5-10MPa, preferably 1-8MPa, and more preferably 2-8 MPa; the reaction temperature is 300-600 ℃, and preferably 370-450 ℃; airspeed of 300-10000h-1Preferably 500--1More preferably 1000--1. The synthesis gas is H2Mixed gas of/CO, H2The molar ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5; the synthesis gas may also contain CO2In which CO is2The volume concentration in the synthesis gas is 0.1-50%.
Based on the technical scheme, the method preferably uses synthesis gas IDirect conversion to C by step method2-4Olefin, C2-4The selectivity of olefin is 50-90%, and the selectivity of byproduct methane is<7％。
Advantageous effects
The technology is different from the traditional technology (MTO for short) for preparing the low-carbon olefin by the methanol, and the synthesis gas is directly converted into the low-carbon olefin by one step.
The preparation process of the composite catalyst provided by the invention is simple and mild in condition, and by embedding the heteroatom into the CHA or AEI structure molecular sieve framework, the activity and product selectivity of the reaction are effectively improved, the reaction conversion rate is improved, the selectivity of olefin is improved, the reaction conversion rate can reach 10-55%, the selectivity of propylene and butylene products in the products is improved, and can reach 40-75%, and C is2-4The selectivity of the low-carbon olefin can reach 50-90%. The product can be separated without deep cooling, the energy consumption and the cost of the separation are greatly reduced, and the selectivity of the byproduct methane is low<7%) and the catalyst has a long life,>700 hours, has good application prospect.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the claims of the invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
The specific surface area of the sample can be measured by nitrogen or argon physical adsorption.
The metal oxide of the present invention can be obtained by purchasing commercially available metal oxides with a high specific surface area, or can be obtained by the following methods:
preparation of catalyst component I
Synthesizing a ZnO material with a high specific surface by a precipitation method:
(1) 3 parts, 0.446g (1.5mmol) of Zn (NO) are weighed out separately3)2·6H2Adding 0.300g (7.5mmol), 0.480g (12mmol) and 0.720g (18mmol) NaOH into 3 containers, respectively, weighing 30ml each to removeAdding the water into 3 containers, stirring at 70 deg.C for more than 0.5 hr to mix the solution uniformly, and naturally cooling to room temperature. Centrifugally separating the reaction liquid, collecting the precipitate after centrifugal separation, and washing the precipitate for 2 times by using deionized water to obtain a ZnO metal oxide precursor;
(2) roasting: and drying the obtained product in air, and roasting in the atmosphere to obtain the ZnO material with high specific surface. The atmosphere is inert gas, reducing gas or oxidizing gas; the inert gas being N2One or more of He and Ar; the reducing gas being H2One or two of CO and the reducing gas can also contain inert gas; the oxidizing gas being O2、O3、NO2And the oxidizing gas may contain an inert gas. The roasting temperature is 300-700 ℃, and the time is 0.5-12 h.
The purpose of calcination is to decompose the precipitated metal oxide precursor into oxide nanoparticles with high specific surface area at high temperature, and the decomposed oxide surface adsorbed species can be treated cleanly by the high-temperature treatment of calcination.
Specific samples and their preparation conditions are shown in Table 1 below, in which ZnO #4 is a commercially available ZnO single crystal of low specific surface area as a comparative example.
TABLE 1 preparation of ZnO materials and their parametric properties
Figure BDA0001916495110000051
(II) synthesizing MnO materials with high specific surface area by a coprecipitation method:
the preparation process is the same as that of ZnO #2, except that a precursor of Zn is replaced by a corresponding precursor of Mn, which can be one of manganese nitrate, manganese chloride and manganese acetate, wherein the precursor is manganese nitrate, and a corresponding product is defined as MnO; the specific surface area is: 23m2/g。
(III) coprecipitation method for synthesizing CeO with high specific surface area2Materials:
the preparation process is the same as the ZnO #2, except that the precursor of Zn is replaced by the corresponding of CeThe precursor of (a) may be one of cerium nitrate, cerium chloride and cerium acetate, herein cerium nitrate, and the corresponding product is defined as CeO2(ii) a The specific surface area is: 92m2/g。
Synthesis of Ga having high specific surface area by coprecipitation method2O3Materials:
the preparation process is the same as that of ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Ga, which can be one of gallium nitrate, gallium chloride and gallium acetate, and the corresponding product is defined as Ga2O3(ii) a The specific surface area is: 55m2/g。
(V) coprecipitation method for synthesizing Bi with high specific surface area2O3Materials:
the preparation process is the same as the ZnO #2, except that the precursor of Zn is replaced by the corresponding precursor of Bi, and the precursor can be one of bismuth nitrate, bismuth chloride and bismuth acetate, and is bismuth nitrate. The corresponding product is defined as Bi2O3(ii) a The specific surface areas are: 87m2/g。
(VI) Synthesis of In having a high specific surface area by coprecipitation2O3Materials:
the preparation process is the same as that of ZnO #2, except that Zn precursor is replaced by corresponding precursor of In, which can be one of indium nitrate, indium chloride and indium acetate, In this case, the corresponding product is defined as In2O3(ii) a The specific surface area is: 52m2/g
(VII) Synthesis of Mn with high specific surface area by precipitationaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)Ox：
Zinc nitrate, aluminum nitrate, chromium nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate and ferric nitrate are used as precursors and mixed with ammonium carbonate in water at room temperature (wherein the ammonium carbonate is used as a precipitator, and the feeding proportion is that the ammonium carbonate is excessive or the proportion of ammonium ions and metal ions is 1:1 preferably); and (3) aging the mixed solution, taking out, washing, filtering and drying, and roasting the obtained solid in an air atmosphere to obtain the metal oxide with the high specific surface, wherein specific samples and preparation conditions thereof are shown in the following table 2.
TABLE 2 preparation of high specific surface area metal oxides and their performance parameters
Figure BDA0001916495110000061
(VIII) dispersant Cr2O3、Al2O3Or ZrO2Dispersed metal oxide
With dispersant Cr2O3、Al2O3Or ZrO2As carrier, preparing Cr by precipitation deposition2O3、Al2O3Or ZrO2A dispersed metal oxide. Taking the preparation of dispersed ZnO as an example, commercial Cr is used2O3(specific surface area about 5 m)2/g)、Al2O3(specific surface area about 20 m)2/g) or ZrO2(specific surface area about 10 m)2/g) as carrier is pre-dispersed in water, then zinc nitrate is used as raw material, mixed with sodium hydroxide precipitant for precipitation at room temperature, Zn2+In a molar concentration of 0.067M, Zn2+The mol part ratio of the organic silicon compound to the precipitant is 1: 8; then aging at 160 ℃ for 24 hours to obtain Cr2O3、Al2O3Or ZrO2ZnO dispersed as a carrier (the content of the dispersant in the component I is 0.1 wt%, 20 wt%, 85 wt% in sequence). The obtained sample is roasted for 1h at 500 ℃ in the air, and the products are sequentially defined as dispersed oxides 1-3, and the specific surface areas are sequentially as follows: 148m2/g，115m2/g，127m2/g。
In the same manner, SiO can be obtained2(specific surface area about 2 m)2/g)、Ga2O3(specific surface area about 10 m)2Per g) or TiO2(specific surface area about 15 m)2(g) MnO oxide dispersed as a support (the content of the dispersant in component I is 5 wt.%, 30 wt.%, 60 wt.% in this order), and the product is defined as dispersed oxide 4 to 6 in this order. The specific surface area is as follows: 97m2/g，64m2/g，56m2/g。
In the same manner, activated carbon (specific surface area about 1000 m) was obtained2Per gram), graphene (specific surface area about 500 m)2Per g) or carbon nanotubes (specific surface area about 300 m)2The ZnO oxide dispersed as a carrier (the content of the dispersant in component I is 5 wt%, 30 wt%, 60 wt% in this order), and the product is defined as a dispersed oxide 7 to 9 in this order. The specific surface area is as follows: 177m2/g，245m2/g，307m2/g。
II, preparation of component II
The CHA and AEI topologies have eight-membered ring apertures, three-dimensional channels.
The present invention is exemplified by molecular sieves prepared by hydrothermal synthesis.
1) The preparation process comprises the following steps:
taking MgSAPO as an example, according to the oxide SiO2:MgO:Al2O3:P2O5:R:H2Weighing the following raw materials in a molar ratio of 0.1:0.3:0.9:1:1.8: 45: silica sol; magnesium nitrate; aluminum hydroxide; phosphoric acid; diisopropylethylamine (DIPEA); deionized water, stirring and aging at 30 ℃, transferring to a hydrothermal kettle after 2 hours, and crystallizing for 120 hours at 180 ℃. And cooling to room temperature, repeatedly centrifuging and washing until the pH value of the supernatant is 7 after washing is finished, drying the precipitate at 110 ℃ for 17h, and roasting at 600 ℃ for 3h to obtain the Mg-doped molecular sieve.
TABLE 3 preparation of heteroatom-doped molecular sieves with AEI topology and their performance parameters
Figure BDA0001916495110000071
Figure BDA0001916495110000081
(II) impregnation method for synthesizing Zr-SAPO, Ba-SAPO and Ce-SAPO molecular sieves
And (3) adding a zirconium nitrate solution with a proper concentration into a 100mL beaker, adding a proper amount of SAPO-18 molecular sieve while stirring, and stirring at room temperature until the mixture is stirred to be dry. And drying and roasting at 600 ℃ for 3h to obtain Zr-SAPO. Ba-SAPO, Ce-SAPO molecular sieve preparation method is the same, metal source is changed into barium nitrate, cerium nitrate.
Preparation of catalyst
The component I and the component II in required proportion are added into a container, the purposes of separation, crushing, uniform mixing and the like are realized by utilizing one or more than two of extrusion force, impact force, shearing force, friction force and the like generated by the high-speed movement of the materials and/or the container, the conversion of mechanical energy, heat energy and chemical energy is realized by regulating the temperature and the carrier gas atmosphere, and the interaction among different components is further regulated.
In the mechanical mixing process, the mixing temperature can be set to be 20-100 ℃, and the mixing can be carried out in an atmosphere or directly in air, wherein the atmosphere is selected from any of the following gases:
a) nitrogen and/or inert gas;
b) a mixed gas of hydrogen and nitrogen and/or inert gas, wherein the volume of the hydrogen in the mixed gas is 5-50%;
c) the mixed gas of CO and nitrogen and/or inert gas, wherein the volume of CO in the mixed gas is 5-20%;
d)O2mixed with nitrogen and/or inert gases, in which O2The volume of the inert gas in the mixed gas is 5-20%, and the inert gas is one or more than two of helium, argon and neon.
The mechanical mixing can be one or more of mechanical stirring, ball milling, table mixing and mechanical grinding, and specifically comprises the following steps:
mechanical stirring: in the stirring tank, the component I and the component II are mixed by a stirring rod, and the mixing degree of the component I and the component II can be adjusted by controlling the stirring time (5min-120min) and the stirring speed (30-300 r/min).
Ball milling: the grinding material and the catalyst are rolled in a grinding tank at a high speed to generate strong impact and rolling on the catalyst, so that the effects of dispersing and mixing the component I and the component II are achieved. By controlling the abrasive (the material can be stainless steel, agate and quartz, and the size range is 5mm-15 mm). The ratio of the catalyst to the catalyst (mass ratio range: 20-100: 1).
A shaking table mixing method: premixing the component I and the component II, and filling the mixture into a container; mixing the component I and the component II by controlling the reciprocating oscillation or the circumferential oscillation of the shaking table; the uniform mixing is realized by adjusting the oscillation speed (range: 1-70 r/min) and the time (range: 5min-120 min).
Mechanical grinding method: premixing the component I and the component II, and filling the mixture into a container; the homogeneous mixing was achieved by relative motion of the attrition tool with the mixed catalyst at a pressure (range: 5 kg-20 kg) (rate range: 30-300 rpm), the specific catalyst preparation and its parametric characteristics are shown in table 6.
TABLE 6 preparation of the catalysts and their parametric characterization
Figure BDA0001916495110000091
Figure BDA0001916495110000101
Figure BDA0001916495110000111
Figure BDA0001916495110000121
Examples of catalytic reactions
Fixed bed reactions are exemplified, but the catalyst is also suitable for use in moving bed reactors. The device is provided with a gas mass flow meter and an on-line product analysis chromatograph (tail gas of a reactor is directly connected with a quantitative valve of the chromatograph to carry out periodic real-time sampling analysis).
2g of the catalyst of the present invention was placed in a fixed bed reactor, and the air in the reactor was replaced with Ar, followed by H2Raising the temperature to 300 ℃ in the atmosphere, and switching the synthesis gas (H)2The mol ratio of/CO is 0.2-3.5), the pressure of the synthetic gas is 0.5-10MPa, the temperature is raised to the reaction temperature of 300-. The product was analyzed by on-line chromatographic detection.
Changing temperature, pressure and space velocity and H in syngas2The molar ratio of/CO can vary the reaction properties. Wherein the selectivity sum of propylene and butylene reaches 30-75%, the selectivity sum of low-carbon olefin (ethylene, propylene and butylene can reach 50-90%, the generation of a large amount of methane is avoided due to low surface hydrogenation activity of the catalyst metal compound, and the methane selectivity is low, and specific application and effect data of the catalyst are listed in Table 7.
TABLE 7 specific use of the catalyst and Effect data thereof
Figure BDA0001916495110000122
Figure BDA0001916495110000131
Figure BDA0001916495110000141
Comparative example 1 catalyst component i was ZnO #4 and component ii was GeSAPO.
Comparative example 4 used a catalyst in which the molecular sieve was a commercial SAPO-34 available from southern Kai university catalyst works and the temperature corresponding to the desorption peak of the medium strong acid from NH3-TPD was 390 ℃ and the amount of the medium strong acid sites was 0.6 mol/kg.
The catalyst used in comparative example 5 was a commercial ZSM-5, full pore structure, with Si/Al of 30, available from catalyst works of south opening university.
The reaction results of comparative examples 4 and 5 show that the topology of CHA or AEI and its acid strength are critical for modulation of product selectivity.
The catalyst adopted in comparative example 6 is a sample containing only component I ZnO #1 without molecular sieve, the reaction conversion rate is very low, and the product is mainly composed of dimethyl ether, methane and other by-products, and almost no ethylene is generated.
The catalyst used in comparative example 7 was a component II only, component 1 molecular sieve, and the sample containing no component I, and the catalytic reaction was almost inactive.
Comparative examples 6 and 7 have only component I or component II on the surface, and have extremely poor reaction effect, and do not have the excellent reaction performance of the invention at all.
The molecular sieve in the catalyst used in comparative example 8 is a self-synthesized SAPO-18, and the remaining parameters and mixing process are the same as catalyst a. The reaction of comparative example 8 has a higher conversion but a poorer selectivity, and the catalyst a doped with Mg on the basis thereof effectively improves the selectivity of the low-carbon olefin.
Comparative example 9 uses a catalyst in which the molecular sieve is Mg (NO)3)2The ion-exchanged SAPO-18, the rest parameters and the mixing process are the same as the catalyst A.
Comparative example 10 uses a catalyst in which the molecular sieve is Ca (NO)3)2The ion-exchanged SAPO-34, the rest parameters and the mixing process are the same as the catalyst B.
The reaction results of comparative examples 9 and 10 show that the SAPO-18 and SAPO-34 samples, which were ion-exchanged, when used as catalyst component B, had significant differences in reaction performance from the heteroatom-doped molecular sieves described herein, and significantly reduced conversion and selectivity. The incorporation of heteroatoms into the framework of SAPO molecular sieves is critical to modulation of reactivity and selectivity.
In the reference (Jiao et al, Science 351(2016)1065-1068) comparison technique, the molecular SAPO-34 sieve acid was used in a relatively large amount, based on NH3TPD test, with a medium strong acid quantity of 0.32mol/kg, thus when the conversion rises to 35%, the selectivity for olefins is 69%, while the selectivity for alkanes is 20%, the ratio of alkenes decreases to 3.5, and the selectivity for propene and butene ranges from 40 to 50%.
From the above table, it can be seen that the structure of the molecular sieve, including the topology of CHA & AEI and its acid strength and acid content, the amount of heteroatom incorporation and whether it is incorporated into the framework, and the matching between the metal oxide and the molecular sieve are critical and directly affect the conversion of carbon monoxide and the selectivity of propene to butene.

Claims (10)

1. A catalyst, characterized by: the catalyst comprises a component I and a component II, wherein the active component of the component I is a metal oxide, and the component II is a doped heteroatom molecular sieve;
the metal oxide is MnOx、MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CeOx、CoaAl(1-a)Ox、FeaAl(1-a)Ox、GaOx、BiOx、InOx、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxOne or more than two of them; the value range of x is 0.7-3.7, and the value range of a is 0-1; the value range of a + b is 0-1;
the molecular sieve is a CHA or AEI topological structure molecular sieve, the framework atoms comprise Al, P, O and Si, and the hetero atoms can be one or more of divalent metals such as Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Zr, Mo, Cd, Ba and Ce, trivalent Ti, Ga and tetravalent Ge; the molecular sieve doped with the heteroatoms is formed by doping the heteroatoms in the molecular sieve framework to replace Al, Si or P in the molecular sieve framework.
2. The catalyst of claim 1, wherein: the MnOx、ZnOx、CeOx、GaOx、BiOx、InOxHas a specific surface area of 1 to 100m2(ii)/g; the preferred specific surface area is 50 to 100m2/g；
The MnaCr(1-a)Ox、MnaAl(1-a)Ox、MnaZr(1-a)Ox、MnaIn(1-a)Ox、ZnOx、ZnaCr(1-a)Ox、ZnaAl(1-a)Ox、ZnaGa(1-a)Ox、ZnaIn(1-a)Ox、CoaAl(1-a)Ox、FeaAl(1-a)Ox、InaAlbMn(1-a-b)Ox、InaGabMn(1-a-b)OxHas a specific surface area of 5 to 150m2A preferred specific surface area is from 50 to 150m2/g。
3. The catalyst of claim 1, wherein: the ratio of the sum of the molar weights of the heteroatoms in the heteroatom-doped molecular sieve to the molar weight of P is 0.001-0.6; the molar weight ratio of Si atoms to P is 0.01-0.6.
4. The catalyst of claim 1, wherein: the weight ratio of the active ingredient in the component I to the component II is 0.1-20, preferably 0.3-5.
5. The catalyst of claim 1, wherein: the component I can also be added with a dispersant, and the metal oxide is dispersed in the dispersant; the dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One or more of activated carbon, graphene and carbon nanotubes; in the component I, the content of the dispersant is 0.05 to 90 weight percent, and the balance is metal oxide.
6. The catalyst of claim 1, wherein: the molecular sieve doped with the heteroatom 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) preparing a sol precursor: dissolving an aluminum source, a phosphorus source and a silicon source in a certain proportion in water, uniformly stirring, adding a precursor containing heteroatoms and a template agent, and stirring for 0.5-12 h; (2) hydrothermal crystallization: carrying out reaction crystallization on the sol precursor obtained in the step (1) at the temperature of 160-200 ℃ for 4-7 days; (3) separation and washing: centrifuging, washing and drying a product after the crystallization reaction; (4) drying and roasting; roasting the product obtained in the step (3) at the temperature of 550-600 ℃ for 3-6 h; the molar ratio of the heteroatom precursor heteroatom to the phosphorus source is 0-0.6%; the post-treatment method comprises the following steps: preparing a solution of a heteroatom precursor, soaking the SAPO-18 or SAPO-34 molecular sieve in the precursor solution, drying, and finally roasting at 550-600 ℃ for 3-6 h.
7. The catalyst of claim 6 wherein the aluminum source is boehmite, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum isopropoxide; the silicon source is silica sol, TEOS, white carbon black, quartz sand and silicate; the heteroatom precursor is metal nitrate, sulfate, acetate, halide and oxide; the template agent is Triethylamine (TEA) and Diisopropylethylamine (DIPEA).
8. A method for preparing low-carbon olefin by catalyzing synthesis gas with high selectivity is characterized by comprising the following steps: the synthesis gas is used as a reaction raw material, and a conversion reaction is carried out on a fixed bed or a moving bed to prepare the low-carbon olefin, wherein the catalyst adopted by the method is the catalyst in claim 1.
9. The method of claim 8, wherein: the pressure of the synthesis gas in the method is 0.5-10MPa, preferably 1-8MPa, and more preferably 2-8 MPa; the reaction temperature is 300-600 ℃, and preferably 370-450 ℃; airspeed of 300-10000h-1Preferably 500--1More preferably 1000--1(ii) a The synthesis gas is H2Mixed gas of/CO, H2The molar ratio/CO is between 0.2 and 3.5, preferably between 0.3 and 2.5; the synthesis gas may also contain CO2，CO2The volume concentration in the synthesis gas is 0.1-50%.
10. The method of claim 9, wherein the method is used for preparing C by directly converting synthesis gas in one step2-4Olefin, C2-4The selectivity of olefin is 50-90%, and the selectivity of byproduct methane is<7％。
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