CN108927132A - A kind of method of bifunctional catalyst and co hydrogenation ethylene - Google Patents

A kind of method of bifunctional catalyst and co hydrogenation ethylene Download PDF

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CN108927132A
CN108927132A CN201710382250.XA CN201710382250A CN108927132A CN 108927132 A CN108927132 A CN 108927132A CN 201710382250 A CN201710382250 A CN 201710382250A CN 108927132 A CN108927132 A CN 108927132A
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catalyst
ethylene
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CN108927132B (en
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包信和
焦峰
潘秀莲
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention belongs to co hydrogenations directly to prepare ethylene, more particularly to a kind of method of bifunctional catalyst and co hydrogenation ethylene, it is using carbon monoxide and hydrogen mixed gas as reaction raw materials, conversion reaction is carried out in fixed bed or moving bed, the catalyst is composite catalyst, it is combined with each other in a manner of mechanical mixture by component A and B component, the active ingredient of component A is metal oxide, and B component is the molecular sieve of the MOR structure of organic alkali modification；The weight ratio between active ingredient and B component in component A is between 0.1-20 range, preferably 0.3-8.Reaction process has very high product yield and selectivity, and C2-C3 olefine selective is up to 78-87%, wherein hydrocarbon products more than 4 C atoms is selectively lower than 10%, byproduct methane it is selectively extremely low (<9%), while ethylene selectivity reaches 75-82%, has a good application prospect simultaneously.

Description

A kind of method of bifunctional catalyst and co hydrogenation ethylene
Technical field
The invention belongs to the high-valued product such as co hydrogenation producing light olefins, and in particular to a kind of bifunctional catalyst And the method for co hydrogenation ethylene.
Background technique
Ethylene is very important basic chemical raw materials, is one of maximum chemical products of yield in the world, ethylene industry It is the core of petrochemical industry, occupies an important position in national economy.Low-carbon alkene refers to that carbon atom number is less than or waits In 4 alkene.It is very important basic organic chemical industry raw material using ethylene, propylene as the low-carbon alkene of representative, as China passes through The rapid growth of Ji, ethylene industry development in China's is swift and violent, and in the world, Market for Ethylene occupies an important position.For a long time, low-carbon Supply falls short of demand in alkene market.Currently, the production of ethylene mainly uses naphtha, the petrochemical industry route of Pyrolysis Reaction of Gas Oil or second The technology of alkane cracking, since China's oil relies on import for a long time, the energy security in China there are greater risk, develop not by urgent need Rely on the ethylene of petroleum.By coal, natural gas, biomass and other recyclable materials etc. be converted into carbon monoxide and Gaseous mixture, that is, synthesis gas of hydrogen, carbon monoxide is different and different with raw material with the ratio of hydrogen in synthesis gas；Again with these Synthesis gas is raw material, after the ratio to suitable value by adjusting carbon monoxide and hydrogen, makes carbon monoxide and hydrogen suitable Catalyst action under, by Fischer-Tropsch synthesis directly be made carbon atom number less than or equal to 4 low-carbon alkene process, this Sample can produce alkene with a step, which produces ethylene for naphtha pyrolysis technology and provide an alternative solution.The technique without Alkene need to be further prepared, simplification of flowsheet greatly reduces as indirect method technique from synthesis gas through methanol or dimethyl ether Investment.
It is always one of the research hotspot that synthesis gas directly produces alkene by the direct preparing low-carbon olefins of F- T synthesis. In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIAs such as MgO alkali metal oxide or high silicon Iron-Mn catalyst system that zeolite molecular sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent with highly basic K or Cs ion, in synthesis gas system Low-carbon alkene reaction pressure is 1.0~5.0MPa, at 300~400 DEG C of reaction temperature, can get higher active (CO conversion ratio 90%) and it is selective (selectivity of light olefin 66%).In the patent ZL03109585.2 that Beijing University of Chemical Technology is declared, use Vacuum impregnation technology prepares the Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent and reacts for preparation of low carbon olefines by synthetic gas, Under conditions of no unstripped gas recycles, CO conversion ratio 96%, selectivity 68% of the low-carbon alkene in hydrocarbon.Above-mentioned report The catalyst in road is to use metallic iron or cementite for active component, and reaction follows the chain propagation reaction mechanism of metal surface, The selectivity of product low-carbon alkene is lower, and especially the selectivity of single product such as ethylene is lower than 30%.2016, Shanghai height etc. was ground Study carefully institute Sun Yuhan researcher and Zhong Liangshu researcher reports a kind of preferentially exposure [101] and [020] manganese and helps carbonization cobalt-based catalyst Agent realizes under 31.8% CO conversion ratio, 60.8% selectivity of light olefin, and methane selectively 5%.But ethylene list One selectivity is but lower than 20%.Dalian Inst of Chemicophysics, Chinese Academy of Sciences's packet letter and academician and Pan Xiulian researcher report The ZnCr of alumina load2O4Oxide and the compound bifunctional catalyst of multi-stage porous SAPO-34 molecular sieve (Jiao et al., Science 351 (2016) 1065-1068), when realizing CO conversion ratio 17%, the selectivity of low-carbon alkene 80%, but ethylene Selectivity be lower than 30%.In the patent 201710129620.9 that they apply, using multiple containing oxygen vacancies and MOR molecular sieve The bifunctional catalyst of conjunction is used for one step olefine reaction of synthesis gas, and the selectivity of ethylene is improved to 75-80%, but by-product Middle carbon atom number be more than 3 hydro carbons it is more, affect the application of the technology.And the present invention further passes through modulation MOR molecular sieve Acid feature, make the selectivity of methane byproduct be further reduced to 9% hereinafter, and C4 or more hydrocarbon selective also into one Step reduces.
Summary of the invention
The technology of the present invention solves the problems, such as：Overcome the deficiencies of the prior art and provide a kind of bifunctional catalyst and carbon monoxide The method for adding hydrogen ethylene, the catalyst invented can catalytic CO and hydrogen reaction directly generate low-carbon alkene, and The selectivity of C2-C3 alkene is up to 78-87%, and the selectivity of single product ethylene may be up to 75-82%, and methane selectively is lower than 9%, C4 and the above hydrocarbon selective are lower than 10%.
The technical scheme is that：A kind of catalyst is combined with each other in a manner of mechanical mixture by component A and B component, The active ingredient of component A is metal oxide, and B component is the molecular sieve of MOR topological structure, it is characterised in that：In B component, institute The molecular sieve for stating MOR topological structure is modified using fatty amine.
The fatty amine be dimethylamine, trimethylamine, diethylamine, triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), It is isopropylamine, diisopropylamine, 1,2- dimethyl propylamine, 1,2- propane diamine, 2- allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, different One of butylamine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice hexylamine, 2 ethyl hexylamine, hexamethylene diamine, trioctylamine or It is two or more.
Using heterocyclic compound can to avoid organic base molecule enter 8 annulus ducts, but selectivity occupy 12 annulus B acid site.And between use bit-by-bit replace molecule can be contacted to avoid organic base caused by space steric effect with B acid compared with It is weak, the problem of absorption loosely.
Between 0.1-20 times of range, weight ratio is preferably the weight ratio between active ingredient and B component in component A 0.3-8；Multicomponent collaboration could to react effective progress, one of excessive or very few progress that can be all unfavorable for reaction.
Metal oxide is made of the crystal grain that size is 5-30nm, is from grain surface to intra-die direction depth In the distance range of 0.3nm, there are a large amount of oxygen vacancies, i.e., oxygen atom mole is reasonable by stoichiometric ratio oxygen molar content 80% hereinafter, it is preferred that oxygen atom the mole reasonable 80%-10% by stoichiometric ratio oxygen molar content, more preferably 60- 10%, most preferably 50-10%；Surface Lacking oxygen is defined as that (1- oxygen atom mole is reasonable to be contained by stoichiometric ratio oxygen mole Amount), corresponding oxygen vacancy concentration is preferably 20-90%, more preferably 40-90%, most preferably 50-90%.
Dispersing agent, dispersing agent Al are also added in component A2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One of or Two kinds, metal oxide dispersion is in dispersing agent, and content of the dispersing agent in component A is in 0.05-90wt%, preferably 0.05- 25wt%, remaining is metal oxide.
The MOR topological structure is a kind of rhombic system, has the one-dimensional channels for the oval straight channels being parallel to each other Structure contains 8 annulus pockets and 12 annulus one-dimensional channels.
The backbone element composition of the molecular sieve with MOR topological structure can be Si-Al-O, Ga-Si-O, Ga-Si- One of Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O or two kinds or more.
The preparation process of metal oxide is：Using in the etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrate One or two or more kinds, metal oxide is soaked in etchant solution；Above-mentioned suspended matter is heated at 100-150 DEG C 30-90 minutes, washing filtering is then taken out, the metal oxide materials with exhibiting high surface oxygen vacancies are obtained；Filtrate is existed Dry reduction treatment in atmosphere, atmosphere are inert gas or inert gas and reducing atmosphere gaseous mixture, inert gas N2、 One of He and Ar or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, in gaseous mixture inert gas with The volume ratio of reducibility gas is 100/10~0/100, is handled 0.5-5 hours, and treatment temperature is 20-350 DEG C.
The method that the fatty amine is modified is first to control temperature on vacuum line and be dehydrated to sieve sample to take off 350-500 DEG C of gas disposal temperature, pressure 1Pa-10-5Pa, time 4h-24h are further exposed to 10Pa- to the molecular sieve of degassing In the atmosphere of the organic base of 100kPa or in the atmosphere of the diluted organic base of inert gas, control adsorption temp is room temperature -300 DEG C, and the molecular sieve of organic alkali modification is obtained after carrying out purging 30min-12h at 200-330 DEG C with inorganic gas.
Mechanical stirring, ball milling, shaking table mixing, one of mechanical lapping or two kinds can be used with enterprising in the mechanical mixture Row is compound.
The method that the gaseous mixture of a kind of carbon monoxide and hydrogen directly converts ethylene processed is related to carbon monoxide and hydrogen Gaseous mixture is reaction raw materials, can also contain a certain amount of carbon dioxide in synthesis gas, be turned in fixed bed or moving bed Change reaction, ethylene can be generated with high selectivity, used catalyst is above-mentioned catalyst.
The pressure of gaseous mixture is 0.5-10MPa, preferably 1-8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 300-450 DEG C；Air speed is 300-10000h-1, preferably 500-9000h-1, more preferably 500-6000h-1, can To obtain higher space-time yield.
The reaction mixture gas H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5, when can obtain higher CO can also be contained in empty yield and selective gaseous mixture2, wherein CO2Volumetric concentration in synthesis gas is 0.1-50%.
The dual-function composite catalyst directly converts ethylene processed or the alkene of C2-C3 for one-step method from syngas, Wherein the selectivity of C2-C3 alkene is up to 78-87%, and ethylene selectivity reaches 75-82%, with byproduct methane selectivity when going back Extremely low (<9%), C4 and the above hydrocarbon selective are lower than 10%.
The invention has the advantages that：
(1) present invention is different from traditional preparing light olefins from methanol technology (referred to as MTO), and realizing a step will directly close Ethylene processed is converted at gas.
(2) the single selectivity of product of ethylene is high in product of the present invention, can reach 75-82%, and high (the alkene receipts of space-time yield Rate up to 1.33mmol/hg), product is easily isolated, and is had a good application prospect.
(3) catalyst of the present invention and 201610600945.6 and 201710129620.9 difference of patent application above-mentioned It is, component B is modified using fatty amine in catalyst of the present invention, is catalyzed and synthesized gas and is converted to obtain the choosing of single component ethylene Selecting property is up to 75-82%, and methane is lower than 9%, and the selectivity for greatly suppressing the hydro carbons of C4 or more is lower than 10%, and preceding State in 201610600945.6 and 201710129620.9 catalyst its to be catalyzed reaction result be that product is wider, methane and C4 with Upper hydro carbons is more, is not able to satisfy the condition.
Specific embodiment
The present invention is further elaborated below by embodiment, but scope of the presently claimed invention is not by these realities Apply the limitation of example.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but is not meant to must satisfy these Condition just can achieve this purpose.
Embodiment 1
One, the preparation of component A
(1) etching method synthesis has the ZnO material of polar surfaces：
(1) 4 parts, every part of 0.446g (1.5mmol) Zn (NO are weighed respectively3)2·6H2O is in 4 containers, then weighs respectively 0.300g (7.5mmol), 0.480g (12mmol), 0.720g (18mmol), 1.200g (30mmol) NaOH sequentially add above-mentioned 4 In a container, then each 30ml deionized water that measures is added in 4 containers, and stirring 0.5h or more is uniformly mixed solution.Heating It is 160 DEG C, reaction time 20h to temperature, precipitating resolves into zinc oxide；Cooled to room temperature.Reaction solution centrifuge separation is received Sediment after collection centrifuge separation, is washed with deionized 2 acquisition ZnO oxides；
The product of wherein 0.480g (12mmol) NaOH dosage is taken to carry out following processing：
(2) super with ZnO oxide at normal temperature using etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrates Sound mixes, and ZnO oxide is soaked in etchant solution, and etching agent and zinc oxide form complexing or direct reduction reactor；
Above-mentioned suspended matter is heated, washing filtering is then taken out, obtains the nano-ZnO material with exhibiting high surface oxygen vacancies Material.
In table 1：The mass ratio of catalyst and etching agent is 1:3.The mass ratio of oleic acid and methenamine is 1:1, it is not molten Agent, the mass ratio of oleic acid -5wt% hydrazine hydrate are 95:5, without solvent；When specific treatment conditions include etching agent, temperature, processing Between and atmosphere type it is as shown in table 1 below.
(3) dry or dry and reduction
The product of above-mentioned acquisition is by centrifugation or filtering, after being cleaned with deionized water, be dried in atmosphere or Dry and reduction treatment, atmosphere are inert gas or inert gas and reducing atmosphere gaseous mixture, inert gas N2, He and One of Ar or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, indifferent gas in dry reduction gaseous mixture The volume ratio of body and reducibility gas is 100/10~0/100, and dry and reduction treatment temperature is 350 degrees Celsius, and the time is 4h.Obtain the ZnO material that surface is rich in Lacking oxygen.Specific sample and its preparation condition such as the following table 1.Wherein surface Lacking oxygen is fixed Justice is (1- oxygen atom mole is reasonable to discuss stoichiometric ratio oxygen molar content).
The preparation and its performance parameters of 1 ZnO material of table
It is in the distance range of 0.3nm that the surface Lacking oxygen, which is from grain surface to intra-die direction depth, and oxygen is former The reasonable percentage by stoichiometric ratio oxygen molar content of sub- mole；
As a comparison case, ZnO4 of the surface without Lacking oxygen without (2) step etching, and the metal that Zn is restored completely Zn 5；
(2), etching method synthesis has the MnO material of polar surfaces：Preparation process corresponds to (1) in above-mentioned (one) The product of 0.480g (12mmol) NaOH dosage and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Mn Presoma, can be one of manganese nitrate, manganese chloride, manganese acetate, be herein manganese nitrate.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen The catalyst in vacancy；Surface Lacking oxygen 67%；
Corresponding product is defined as MnO 1；
(3) etching method synthesis has the CeO of polar surfaces2Material：Preparation process corresponds to (1) in above-mentioned (one) The product of 0.480g (12mmol) NaOH dosage and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Ce Presoma, can be one of cerous nitrate, cerium chloride, cerous acetate, be herein cerous nitrate.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen The catalyst in vacancy；Surface Lacking oxygen 56%；
Corresponding product is defined as CeO 1；
(4) synthesis has the nanometer Zn Cr of high-specific surface area, high surface energy2O4、ZnAl2O4、MnCr2O4、MnAl2O4, MnZrO4Spinelle：
Use zinc nitrate, aluminum nitrate, chromic nitrate, manganese nitrate, zirconium nitrate for presoma, with the urea phase in water at room temperature Mutually mixing；Above-mentioned mixed liquor is aged, washing, filtering and drying are then taken out, resulting solid is roasted in air atmosphere, obtained Obtain the spinel oxide along the growth of (110) crystal plane direction.Sample also passes through etching method processing, and synthesis has exhibiting high surface oxygen empty The catalyst of position；Etching processing and last handling process with described in (2) and (3) in above-mentioned (one), the sample have bigger serface, Surface defect is more, can be applied to catalyze and synthesize gas conversion.
Specific sample and its preparation condition such as the following table 2.Equally, surface Lacking oxygen is defined as that (1- oxygen atom mole is reasonable By stoichiometric ratio oxygen molar content).
The preparation and its performance parameter of 2 spinel of table
(5) synthesis has the nanometer Fe Al of high-specific surface area, high surface energy2O4、CoAl2O4Spinelle：Preparation process is same (2) in above-mentioned (four) are described, can be nitre the difference is that the presoma of Zn to have been changed into the corresponding presoma of Fe or Co One of sour iron, iron chloride, ironic citrate or one of cobalt nitrate, cobalt chloride, cobalt acetate are herein ferric nitrate, nitre Sour cobalt.
Described in 3 preparation process of product ZnO of the etch processes with (2) in above-mentioned (one), synthesis has exhibiting high surface oxygen The catalyst in vacancy；Surface Lacking oxygen 77%, 51%；
Corresponding product is defined as spinelle 6, spinelle 7；
(6) Cr2O3、Al2O3Or ZrO2The metal oxide of dispersion
With Cr2O3、Al2O3Or ZrO2For carrier, precipitates sedimentation and prepare Cr2O3、Al2O3Or ZrO2The metal of dispersion aoxidizes Object.For dispersing the preparation of ZnO oxide, by business Cr2O3、Al2O3Or ZrO2Carrier is scattered in advance in the liquid of bottom, is then adopted It is raw material with zinc nitrate, with sodium hydroxide pellets agent mixed precipitation at room temperature, Zn2+Molar concentration be 0.1M, Zn2+With it is heavy The molfraction ratio of shallow lake agent is 1：6；Then it is aged 24 hours at 120 DEG C, obtains Cr2O3、Al2O3Or ZrO2For support dispersion ZnO oxide.
Described in 3 preparation process of product ZnO of the etching process with (2) in above-mentioned (one), synthesis has exhibiting high surface Lacking oxygen Catalyst (content of the dispersing agent in component A is followed successively by 0.2wt%, 10wt%, 90wt%)；Surface Lacking oxygen 25%, 30%, 65%；Last handling process is the same as described in (3) in above-mentioned (one)；
Product is corresponded to from top to bottom is defined as dispersal oxide 1-3；
In the same way, Cr can be obtained2O3、Al2O3Or ZrO2For the MnO oxide of support dispersion, (dispersing agent is in urging Content in agent A is followed successively by 7wt%, 30wt%, 60wt%), surface Lacking oxygen 22%, 47%, 68%；It corresponds to from top to bottom Product is defined as dispersal oxide 4-6.
Two, the preparation of B component (molecular sieve of MOR topological structure)
The MOR topological structure is a kind of rhombic system, has the one-dimensional channels for the oval straight channels being parallel to each other Structure contains 8 annulus one-dimensional straight channels parallel with 12 annulus, and there are 8 annulus pockets to be connected to for 12 annulus main aperture road sides.
Specifically preparation process is：
According to n (SiO2)/n(Al2O3)=15, n (Na2O)/n(SiO2)=0.2, n (H2O)/n(SiO2)=26.
Aluminum sulfate is mixed with sodium hydroxide solution, silica solution is then added, stirring 1h obtains the Primogel of homogeneous phase, It transfers it in Autoclaves for synthesis, 180 DEG C of static crystallizations are quenched afterwards for 24 hours, wash, drying to get modenite sample is arrived Product are labeled as Na-MOR.
Take Na-MOR, it mixed with the ammonium chloride solution of 1mol/L, 3h is stirred at 90 DEG C, wash, drying, continuously into Row 4 times, 450 degree of roasting 6h obtain h-mordenite.
By the above process preparation the molecular sieve with MOR topological structure backbone element form can be Si-Al-O, One of Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O；
H is connected on the O element of part skeleton, corresponding product is successively defined as MOR1-8；
Table 3 has the preparation and its performance parameter of the molecular sieve of MOR topological structure
The molecular sieve that will be prepared takes and carries out dehydration degassing process under vacuum in right amount, and 400 DEG C of temperature, pressure 10-4Pa, After being down to 300 DEG C after 10h, it is passed through the organic base gas of 200Pa into vacuum cavity, is taken off at the same temperature after balancing 10h Attached 1h.
By MOR1, MOR2, MOR3, MOR4, MOR5, MOR6, MOR7, MOR 8 successively used：Dimethylamine, trimethylamine, diethyl Amine, triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamine, 1,2- the third two Amine, 2- allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice oneself After amine, 2 ethyl hexylamine, hexamethylene diamine, trioctylamine processing, MOR9, MOR10, MOR11, MOR12, MOR13, MOR14 are respectively obtained, MOR15,MOR16,MOR17,MOR18,MOR19,MOR20,MOR21,MOR22,MOR23,MOR24,MOR25,MOR26, MOR27,MOR28,MOR29,MOR30,MOR31,MOR32。
Three, the preparation of catalyst
The component A of required ratio and B component are added to the container, produced using the high-speed motion of these materials and/or container The mesh such as separation, broken, mixing are realized in the effect of one or more of raw extruding force, impact force, cutting power, frictional force etc. , the conversion of mechanical energy, thermal energy and chemical energy is realized by modulation temperature and carrier gas atmosphere, further between adjusting different component Interaction.
During mechanical mixture, can be set 20-100 DEG C of mixing temperature, can in atmosphere or directly in air It carries out, atmosphere is：A) nitrogen and/or inert gas, b) hydrogen and nitrogen and/or inert gas gaseous mixture, wherein hydrogen in Volume in gaseous mixture is the gaseous mixture of 5~50%, c) CO and nitrogen and/or inert gas, wherein body of the CO in gaseous mixture Product is 5~20%, d) O2With the gaseous mixture of nitrogen and/or inert gas, wherein O2Volume in gaseous mixture is 5-20%, institute Stating inert gas is one or more of helium, argon gas, neon.
Mechanical stirring：In stirred tank, component A and B component are mixed using stirring rod, by controlling mixing time (5min-120min) and rate (30-300 turns/min), the mixability and relative distance of adjustable component A and B component.
Ball milling：It is rolled at a high speed in grinding pot using abrasive material and catalyst, intense impact is generated to catalyst, is rolled, is reached To dispersion, the effect of mixing component A and B component.By control abrasive material, (material can be stainless steel, agate, quartz.Size model It encloses：5mm-15mm) (quality compares range with the ratio of catalyst：20-100:1), the granularity of adjustable catalyst and it is opposite away from From.
Shaking table mixing method：Component A and B component are pre-mixed, and are fitted into container；By control shaking table reciprocating vibration or Circumferential oscillation realizes the mixing of component A and B component；By adjusting hunting speed (range：1-70 revs/min) and time (range： 5min-120min), it realizes and uniformly mixes and adjust its relative distance.
Mechanical milling method：Component A and B component are pre-mixed, and are fitted into container；In certain pressure (range：5 kilograms- 20 kilograms) under, relative motion (speed range is carried out with mixed catalyst by lap tool：30-300 turns/min), reach adjusting Catalyst grain size, relative distance and the mixed uniformly effect of realization.
Specific catalyst preparation and its parameter attribute are as shown in table 4.
The preparation of 4 catalyst of table and its parameter attribute
Catalysis reaction example
By taking fixed bed reaction as an example, but catalyst is also applied for moving-burden bed reactor.The device is equipped with gas mass flow (tail gas of reactor is directly connect with the proportional valve of chromatography, carries out period real-time sampling point for meter, online product analysis chromatography Analysis).
The catalyst 2g of aforementioned present invention is placed in fixed bed reactors, using the air in Ar metathesis reactor, so Afterwards again in H2300 DEG C are warming up in atmosphere, switching and merging gas (H2/ CO molar ratio=0.2-3.5), the pressure of synthesis gas is 0.5- 10MPa is warming up to 300-600 DEG C of reaction temperature, adjusts the air speed of reactor feed gas to 500-8000ml/g/h.Product is by online Chromatography tests and analyzes.
Change temperature, pressure and air speed, thus it is possible to vary reactivity worth.The selectivity of ethylene, propylene in the product is up to 78- 87%, feed stock conversion 10-60%；Since molecular sieve is effectively cooperateed with oxide, methane and C are avoided4+Hydro carbons it is a large amount of It generates.
The application of 5 catalyst of table and its effect
The catalyst that comparative example 3 uses is component A metal ZnCo+MOR26, ZnCo molar ratio 1：1, ZnCo with point 1 mass Than 1：1, remaining parameter and mixed process etc. are the same as catalyst C.
The catalyst that comparative example 4 uses is surface without oxygen vacancies TiO2+ MOR27, remaining parameter and mixed process etc. are same Catalyst C.
It is bright to catalytic performance regulating and controlling effect that the reaction result of comparative example 5 and 6 shows that MOR is post-processed using fatty amine Aobvious, compared to the catalyst regulated and controled without using fatty amine, the catalyst after regulation significantly reduces methane and C4 or more hydro carbons Selectivity, while improving low-carbon alkene and ethylene selectivity.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This The range of invention is defined by the following claims.It does not depart from spirit and principles of the present invention and the various equivalent replacements made and repairs Change, should all cover within the scope of the present invention.

Claims (10)

1. a kind of catalyst, is made of component A and B component, component A and B component are combined with each other in a manner of mechanical mixture, A group The active ingredient divided is metal oxide, and B component is the molecular sieve of MOR topological structure, it is characterised in that：It is described in B component The molecular sieve of MOR topological structure is modified using fatty amine.
2. catalyst according to claim 1, it is characterised in that：The fatty amine be dimethylamine, trimethylamine, diethylamine, Triethylamine, ethylenediamine, a propylamine, di-n-propylamine, tripropyl amine (TPA), isopropylamine, diisopropylamine, 1,2- dimethyl propylamine, 1,2- propane diamine, 2- allylamine, cyclopropylamine, n-butylamine, di-n-butylamine, isobutyl amine, sec-butylamine, 1,4- butanediamine, tert-butylamine, di-iso-butylmanice hexylamine, One or more of 2 ethyl hexylamine, hexamethylene diamine, trioctylamine.
3. catalyst according to claim 1, it is characterised in that：In the active ingredient of the component A, metal oxide is MnO、MnCr2O4、MnAl2O4、MnZrO4、ZnO、ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds More than；Preferably MnO, MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds More than；More preferably MnO, MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more.
4. catalyst according to claim 1, it is characterised in that：Between active ingredient and B component in the component A Weight ratio is 0.1-20, and weight ratio is preferably 0.3-8.
5. catalyst according to claim 1-4, it is characterised in that：The metal oxide from grain surface to Intra-die direction depth is in the distance range of 0.3nm there are Surface Oxygen vacancy, and the surface Lacking oxygen percentage composition is 20% or more, preferably 20-90%, more preferably 40-90%, most preferably 50-90%.
6. catalyst according to claim 1-5, it is characterised in that：Dispersing agent is also added in the component A, The dispersing agent is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3One of or two kinds or more, metal oxide dispersion in In the dispersing agent, for content of the dispersing agent in component A in 0.05-90wt%, preferably 0.05-25wt%, remaining is gold Belong to oxide.
7. according to catalyst described in any one of claims 1-6, it is characterised in that：The bone of the MOR topological structure molecular sieve Frame element composition is Si-Al-O, Ga-Si-O, Ga-Si-Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O One of or two kinds or more.
8. a kind of method of co hydrogenation ethylene, it is characterised in that：It is that reaction is former with carbon monoxide and hydrogen mixed gas Material, conversion reaction is carried out in fixed bed or moving bed, obtains the low-carbon alkene product based on ethylene, used catalyst is Catalyst as claimed in claim 1 to 7.
9. according to the method described in claim 8, it is characterized in that：The pressure of the mixture gas is 0.5-10MPa, preferably 1-8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 300-400 DEG C；Air speed is 300-10000h-1, Preferably 500-9000h-1, more preferably 500-6000h-1。
10. method according to claim 8 or claim 9, it is characterised in that：The gaseous mixture is to contain H2With the gaseous mixture of CO, H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5；CO can also be contained in the gaseous mixture2, wherein CO2In gaseous mixture Volumetric concentration be 0.1-50%.
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