CN109939669A - A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene - Google Patents

A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene Download PDF

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CN109939669A
CN109939669A CN201810081280.1A CN201810081280A CN109939669A CN 109939669 A CN109939669 A CN 109939669A CN 201810081280 A CN201810081280 A CN 201810081280A CN 109939669 A CN109939669 A CN 109939669A
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catalyst
component
ethylene
selectivity
molecular sieve
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CN109939669B (en
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潘秀莲
焦峰
包信和
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention belongs to co hydrogenation directly conversions to prepare ethylene, more particularly to the method for a kind of base-modified composite catalyst and carbon monoxide 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 I and component II, the active ingredient of component I is metal oxide, and component II is the molecular sieve of the MOR structure of organic alkali modification；The weight ratio of active ingredient and component II in component I is 0.1-20.Reaction process has very high product yield and selectivity, C2-C3 olefine selective is up to 83-90%, wherein it is lower than 7% containing hydrocarbon products more than 4 C atoms, byproduct methane is selectively extremely low (< 5%), and ethylene selectivity and space-time yield significantly improve, selectivity reaches 75-85%, has a good application prospect.

Description

A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene
Technical field
The invention belongs to co hydrogenation producing light olefins high level chemicals, and in particular to a kind of base-modified compound to urge The method of agent and carbon monoxide 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 is believed and reports aluminium oxide with Pan Xiulian team The ZnCr of 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 the selectivity of ethylene Lower than 30%.In the patent 201610600945.6 that they apply, using containing oxygen vacancies and the compound double function of MOR molecular sieve Energy catalyst is used for one step olefine reaction of synthesis gas, and the selectivity of ethylene is improved to 30-75%, but carbon atom in by-product Number be more than 3 hydro carbons it is more, affect the application of the technology.And the acidity that the present invention further passes through modulation MOR molecular sieve is special It is low further to make the selectivity of methane byproduct for point, and the selectivity of the hydrocarbon product of C4 or more also further decreases.
Summary of the invention
The technology of the present invention solves the problems, such as: overcoming the deficiencies of the prior art and provide the base-modified catalyst of one kind and an oxidation The method of carbon hydrogenation reaction ethylene, the catalyst invented can catalytic CO add hydrogen directly convert it is highly selective generate it is low Carbon olefin, and the selectivity of C2-C3 alkene is up to 83-90%, and the selectivity of single product ethylene may be up to 75-85%, first Alkane is selectively lower than 5%, C4 and the above hydrocarbon selective lower than 7%.
The technical solution of the present invention is as follows: a kind of catalyst, the catalyst includes components I and compositionⅱ, the components I and Compositionⅱ is combined with each other in a manner of mechanical mixture, and the active ingredient of components I is metal oxide, and compositionⅱ is MOR topology knot The molecular sieve of structure；The molecular sieve of the MOR topological structure is through organic base modification；The modification is to disperse organic base To the B acid site in 12 annulus ducts of the molecular sieve of the MOR topological structure；The organic base is heterocyclic compound；It is preferred that Heteroaryl；Further preferably containing 1-2 heteroatomic heteroaryls；5 or 6 unit's heteroaryls more preferably containing 1-2 N atom.
MOR topological structure of the present invention is a kind of rhombic system, has the one of the oval straight channels being parallel to each other Cellular structure is tieed up, 8 annulus pockets and 12 annulus one-dimensional channels are contained.
One of mechanical stirring, ball milling, shaking table mixing, mechanical lapping or two kinds can be used in mechanical mixture of the present invention It carries out above compound.
The molecular sieve of the MOR topological structure can enter 8 circles through heterocyclic compound modification to avoid organic base molecule Annular distance road, but the B acid site for occupying 12 annulus of selectivity.And the molecule that bit-by-bit replaces between use can be to avoid space bit Organic base caused by inhibition effect contacted with B acid it is weaker, absorption loosely the problem of.
The heterocyclic compound can be furans, thiophene, pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, Yin Diindyl, quinoline, pteridine, acridine.The heterocyclic compound can have methyl, ethyl, amino, one or more of nitro Substituent group.It is preferred that meta position and/or contraposition replace.
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 of or two kinds or more；
The MnOx、ZnOx、CeOx、GaOx、BiOx、InOxSpecific surface area be 1-100m2/g；It is preferred that specific surface area is 50-100m2/g；
The MnaCr(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)OxRatio table Area is 5-150m2/g.It is preferred that specific surface area is 50-150m2/g；
The value range of the x is that the value range of 0.7~3.7, a is 0~1；The value range of a+b is 0~1；
A of the present invention, b, (1-a), (1-a-b), what x only represented that element chemistry in metal oxide forms compares Example, the identical metal oxide of all ratios are considered as same metal oxide.
The weight ratio of active ingredient and compositionⅱ in components I is 0.1-20, preferably 0.3-8, multicomponent collaboration ability So that reaction effectively carries out, one of excessive or very few progress that can be all unfavorable for reaction.
Dispersing agent is also added in the components I, the metal oxide dispersion is in dispersing agent, dispersing agent Al2O3、 SiO2、Cr2O3、ZrO2、TiO2、Ga2O3, active carbon, graphene, one of carbon nanotube or two kinds or more.The components I In, for the content of dispersing agent in 0.05-90wt%, remaining is metal oxide.
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.
Organic alkali modification of the present invention refers to the B acid occupied in 12 annulus duct of MOR molecular sieve using organic base molecule Site, can be fully take up be also possible to part occupy.The B acid site in 12 annulus ducts being occupied is 50-100%
The method that organic base is distributed to the B acid site in the 12 annulus duct of MOR molecular sieve, it is all well known The method that the purpose may be implemented can satisfy requirement, and the present invention is first controlled on vacuum line by taking vacuum dehydration absorption method as an example Temperature processed carries out 350-500 DEG C of degassing process temperature of dehydration, pressure 1Pa-10 to sieve sample-5Pa, time 4h-24h, into one Walk 10Pa-100kPa is exposed to the molecular sieve of degassing organic base atmosphere in or the diluted organic base of inert gas atmosphere In, control adsorption temp is room temperature to be had to 300 DEG C, and after carrying out purging 30min-12h at 200-330 DEG C with inorganic gas The molecular sieve of machine alkali modification.
A kind of method that synthesis gas directly converts ethylene processed, is related to using synthesis gas as reaction raw materials, can be in synthesis gas Containing a certain amount of carbon dioxide, conversion reaction is carried out in fixed bed or moving bed, can generate ethylene, institute with high selectivity The catalyst used is above-mentioned catalyst.
The pressure of synthesis gas 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 synthesis gas H2/ CO molar ratio is 0.2-3.5, and preferably 0.3-2.5 can obtain higher space-time Yield and selectivity.CO can also be contained in synthesis gas2, wherein CO2Volumetric concentration in synthesis gas is 0.1-50%.
The above-mentioned catalyst of the present invention directly converts ethylene processed or the alkene of C2-C3 for one-step method from syngas, wherein C2- The selectivity of C3 alkene is up to 83-90%, and ethylene selectivity reaches 75-85%, with also when byproduct methane it is selectively extremely low (< 5%), C4 and the above hydrocarbon selective are lower than 7%.
The present invention has the advantage 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 75-85%, and high (the alkene receipts of space-time yield Rate up to 1.42mmol/hg), product is easily isolated, and is had a good application prospect.
(3) metal oxide specific surface area with higher in catalyst, therefore have on metal oxide surface more Active site, be more advantageous to catalysis reaction progress.
(4) on the one hand the effect of Components of Catalysts II is to be generated component I active by being coupled with component I Gas phase intermediate, which further converts, obtains low-carbon alkene, since the component II effect pulled to tandem reaction balance can promote group Divide I to the activating conversion of synthesis gas and then improve conversion ratio, molecular sieve is special in the component II that on the other hand present invention uses Cellular structure, have it is unique select type effect, more ethylene products of acquisition that can be highly selective.
(5) function of the invention, example individually be can not achieve completely using heretofore described component I or component II respectively When component I is such as used alone, methane selectively is very high in product, and conversion ratio is very low, and when component II is used alone, almost It is unable to activating conversion synthesis gas, only component I and component II concerted catalysis are just able to achieve efficient synthesis gas and convert, and obtain excellent Different selectivity.This is because component I, which can activate synthesis gas, generates specific active gas phase intermediate, intermediate is via gas phase It is diffused into the duct of component II, due to the molecular sieve for the MOR structure that the present invention selects, there is special cellular structure and acidity The further activating conversion of active gas phase intermediate that effectively component I can be generated is alkene.Due to the special hole of II component Road structure makes product have special selectivity.
(6) Components of Catalysts II of the present invention is modified using heterocycle organic base, catalyze and synthesize gas convert to obtain it is single The selectivity of component ethylene is up to 75-85%, and methane selectively is lower than 5%, and greatly suppress the hydro carbons of C4 or more Selectivity.
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 I component
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.
The specific surface area of sample can be tested by the method for nitrogen or argon gas physical absorption.
Metal oxide of the present invention can be obtained by buying the metal oxide of commercially available high-specific surface area, It can be obtained by following several methods:
One, the preparation of catalytic component I
(1), precipitation method synthesis has the ZnO material of high-ratio surface:
(1) 3 parts, every part of 0.446g (1.5mmol) Zn (NO are weighed respectively3)2·6H2O is in 3 containers, then weighs respectively 0.300g (7.5mmol), 0.480g (12mmol), 0.720g (18mmol) NaOH are sequentially added in above-mentioned 3 containers, then each amount 30ml deionized water is taken to be added in 3 containers, 70 DEG C of stirring 0.5h or more are uniformly mixed solution, cooled to room temperature. The sediment after centrifuge separation is collected in reaction solution centrifuge separation, and 2 acquisition ZnO metallic oxide precursors are washed with deionized Body；
(2) it roasts: after the product of above-mentioned acquisition is dried in air, carrying out calcination process in atmosphere to get height is arrived The ZnO material of specific surface.Atmosphere is inert gas, reducibility gas or oxidizing gas；Inert gas is N2, in He and Ar One or two or more kinds；Reducibility gas is H2, CO one kind or two kinds, can also also contain inert gas in Primordial Qi；Oxygen The property changed gas is O2、O3、NO2One or more of, inert gas can also be contained in oxidizing gas.Maturing temperature is 300-700 DEG C, time 0.5h-12h.
The purpose of roasting is in order to which the metal oxide precursor after precipitating is decomposed into high-specific surface area at high temperature Oxide nano-particles, and it is dry by the oxide surface adsorbing species processing that the high-temperature process of roasting can will decompose generation Only.
Specific sample and its preparation condition such as the following table 1, as a comparison case, ZnO#4 is the ZnO of commercially available low specific surface area in table Monocrystalline.
The preparation and its performance parameters of table 1ZnO material
(2) Co deposited synthesis has the MnO material of high-specific surface area:
Preparation process is with above-mentioned ZnO#2, the difference is that the presoma of Zn has been changed into the corresponding presoma of Mn, it can It is herein manganese nitrate for one of manganese nitrate, manganese chloride, manganese acetate, corresponding product is defined as MnO；Specific surface area is: 23m2/g。
(3) Co deposited synthesis has the CeO of high-specific surface area2Material:
Preparation process is with above-mentioned ZnO#2, the difference is that the presoma of Zn has been changed into the corresponding presoma of Ce, it can It is herein cerous nitrate for one of cerous nitrate, cerium chloride, cerous acetate, corresponding product is defined as CeO2；Specific surface area is: 92m2/g。
(4) Co deposited synthesis has the Ga of high-specific surface area2O3Material:
Preparation process is with above-mentioned ZnO#2, the difference is that the presoma of Zn has been changed into the corresponding presoma of Ga, it can It is herein gallium nitrate for one of gallium nitrate, gallium chloride, acetic acid gallium, corresponding product is defined as Ga2O3；Specific surface area is: 55m2/g。
(5) Co deposited synthesis has the Bi of high-specific surface area2O3Material:
Preparation process is with above-mentioned ZnO#2, the difference is that the presoma of Zn has been changed into the corresponding presoma of Bi, it can It is herein bismuth nitrate for one of bismuth nitrate, bismuth chloride, bismuth acetate.Corresponding product is defined as Bi2O3；Specific surface area difference It is: 87m2/g。
(6) Co deposited synthesis has the In of high-specific surface area2O3Material:
Preparation process is with above-mentioned ZnO#2, the difference is that the presoma of Zn has been changed into the corresponding presoma of In, it can It is herein indium nitrate for one of indium nitrate, inidum chloride, indium acetate, corresponding product is defined as In2O3；Specific surface area is: 52m2/g
(7) precipitation method synthesis has the Mn of high-specific surface areaaCr(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:
Use zinc nitrate, aluminum nitrate, chromic nitrate, manganese nitrate, zirconium nitrate, indium nitrate, cobalt nitrate, ferric nitrate for presoma, With ammonium carbonate, at room temperature Yu Shuizhong be mutually mixed (wherein ammonium carbonate is as precipitating reagent, ingredient proportion be ammonium carbonate it is excessive or It is preferred that the ratio of ammonium ion and metal ion is 1:1)；Above-mentioned mixed liquor is aged, washing, filtering and drying, institute are then taken out The solid obtained roasts in air atmosphere, obtains the metal oxide of high-ratio surface, specific sample and its preparation condition such as following table 2。
The preparation and its performance parameter of 2 metal in height ratio surface area oxide of table
(8), dispersing agent C r2O3、Al2O3Or ZrO2The metal oxide of dispersion
With dispersing agent C r2O3、Al2O3Or ZrO2For carrier, precipitates sedimentation and prepare Cr2O3、Al2O3Or ZrO2The gold of dispersion Belong to oxide.By taking the preparation for dispersing ZnO as an example, by business Cr2O3(specific surface area is about 5m2/g)、Al2O3(specific surface area is about 20m2/ g) or ZrO2(specific surface area is about 10m2/ g) it is dispersed in water in advance as carrier, then use zinc nitrate for raw material, With sodium hydroxide pellets agent mixed precipitation at room temperature, Zn2+Molar concentration be 0.067M, Zn2+With the molfraction of precipitating reagent Than for 1:8；Then it is aged 24 hours at 160 DEG C, obtains Cr2O3、Al2O3Or ZrO2For the ZnO of support dispersion, (dispersing agent is in group The content in I is divided to be followed successively by 0.1wt%, 20wt%, 85wt%).Obtained sample 500 DEG C of roasting 1h under air, product according to Secondary to be defined as dispersal oxide 1-3, specific surface area is successively are as follows: 148m2/ g, 115m2/ g, 127m2/g。
In the same way, SiO can be obtained2(specific surface area is about 2m2/g)、Ga2O3(specific surface area is about 10m2/g) Or TiO2(specific surface area is about 15m2/ g) be support dispersion MnO oxide (content of the dispersing agent in components I is followed successively by 5wt%, 30wt%, 60wt%), product is successively defined as dispersal oxide 4-6.Its specific surface area is successively are as follows: 97m2/ g, 64m2/ G, 56m2/g。
In the same way, active carbon can be obtained (specific surface area is about 1000m2/ g), (specific surface area is about graphene 500m2/ g) or carbon nanotube (specific surface area is about 300m2/ g) be support dispersion ZnO oxide (dispersing agent is in components I Content is followed successively by 5wt%, 30wt%, 60wt%), product is successively defined as dispersal oxide 7-9.Its specific surface area is successively are as follows: 177m2/ g, 245m2/ g, 307m2/g。
Two, the preparation of II 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.
MOR molecular sieve of the present invention can be the commodity molecular sieve directly bought, and be also possible to point voluntarily synthesized Son sieve.Used here as Catalyst Factory, Nankai Univ production MOR molecular sieve as MOR1；Also voluntarily pass through hydrothermal synthesis method simultaneously For be prepared for 7 molecular sieves with MOR structure；
Specific preparation process are as follows:
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.
MOR1 is successively used: furans, thiophene, pyrroles, thiazole, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline Quinoline, pteridine, acridine handle to obtain MOR9-21.
In order to illustrate the modification of the heterocyclic compound containing substituent group, MOR2 is obtained into MOR22 through 1- methylfuran； MOR3 handles to obtain MOR23 through 1- methylpyrrole；MOR4 handles to obtain MOR24 through 3,5- lutidines；MOR5 is through 4- ethyl pyrrole Pyridine handles to obtain MOR25；MOR6 handles to obtain MOR26 through 3- methylquinoline；MOR7 handles to obtain by 4- methyl indol MOR27；MOR8 handles to obtain MOR28 by 5- methylacridine.
Three, the preparation of catalyst
The components I of required ratio and compositionⅱ 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 selected from following arbitrary gas:
A) nitrogen and/or inert gas；
B) gaseous mixture of hydrogen and nitrogen and/or inert gas, wherein volume of the hydrogen in gaseous mixture is 5~50%；
C) gaseous mixture of CO and nitrogen and/or inert gas, wherein volume of the CO in gaseous mixture is 5~20%；
d)O2With the gaseous mixture of nitrogen and/or inert gas, wherein O2Volume in gaseous mixture is 5-20%, described lazy Property gas be one or more of helium, argon gas, neon.
One of mechanical stirring, ball milling, shaking table mixing, mechanical lapping can be used in mechanical mixture or two kinds or more are answered It closes, specific as follows:
Mechanical stirring: in stirred tank, being mixed components I and compositionⅱ using stirring rod, when being stirred by control Between (5min-120min) and rate (30-300 turns/min), the mixability of adjustable components I and compositionⅱ.
Ball milling: being rolled at a high speed in grinding pot using abrasive material and catalyst, is generated intense impact to catalyst, is rolled, reaches To dispersion, the effect of mixed component I and compositionⅱ.By control abrasive material, (material can be stainless steel, agate, quartz.Size model It encloses: 5mm-15mm).With the ratio of catalyst (quality is than range: 20-100:1).
Shaking table mixing method: components I and compositionⅱ are pre-mixed, and are fitted into container；By the reciprocating vibration for controlling shaking table Or circumferential oscillation, realize the mixing of components I and compositionⅱ；By adjusting hunting speed (range: 1-70 revs/min) and time (model Enclose: 5min-120min), realize uniformly mixing.
Mechanical milling method: components I and compositionⅱ are pre-mixed, and are fitted into container；In certain pressure, (range: 5 is public - 20 kilograms of jin) under, relative motion (speed range: 30-300 turns/min) is carried out with mixed catalyst by lap tool, is realized equal Even mixed effect.
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 83- 90%, feed stock conversion 10-60%；Since molecular sieve effectively acts synergistically with oxide, a large amount of generations of methane are avoided, Methane selectively is lower than 5%, and wherein the selectivity of ethylene reaches 75-85%.
The application of 5 catalyst of table and its effect
The component I for the catalyst that comparative example 2 uses is metal ZnCo, ZnCo molar ratio 1:1, remaining parameter and mixed process Deng with catalyst C.
The component I for the catalyst that comparative example 3 uses is TiO2, remaining parameter and mixed process etc. are the same as catalyst C.
The reaction result of comparative example 4-11 shows that MOR is modified processing to catalytic performance regulating and controlling effect using organic base Obviously, compared to the catalyst regulated and controled without using organic base, the catalyst after regulation significantly reduces methane and C4 or more hydrocarbon The selectivity of class, while improving low-carbon alkene and ethylene selectivity.
The catalyst that comparative example 12 uses is only component I, is ZnO#1, the sample without containing MOR molecular sieve, reaction turn Rate is very low, and product is mainly with dimethyl ether, based on the by-products such as methane, almost without ethylene synthesis.
The catalyst that comparative example 13 uses is only component II, is MOR9 molecular sieve, the sample without containing component I, catalysis Reaction is almost without activity.
Comparative example 12,13 shows that reaction effect is extremely poor when only component I or component II, does not have of the present invention completely Excellent reactivity worth.
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, it is characterised in that: the catalyst includes components I and compositionⅱ, and the components I and compositionⅱ are with machine Tool hybrid mode is combined with each other, and the active ingredient of components I is metal oxide, and compositionⅱ is the molecular sieve of MOR topological structure； The molecular sieve of the MOR topological structure is through organic base modification；The modification is that organic base is distributed to the MOR to open up Flutter the B acid site in 12 annulus ducts of the molecular sieve of structure；The organic base is heterocyclic compound；It is preferred that heteroaryl；Into one Step is preferably containing 1-2 heteroatomic heteroaryls；5 or 6 unit's heteroaryls more preferably containing 1-2 N atom.
2. catalyst according to claim 1, it is characterised in that: the heterocyclic compound is furans, thiophene, pyrroles, thiophene Azoles, imidazoles, pyridine, pyrazine, pyrimidine, pyridazine, indoles, quinoline, pteridine or acridine；It is preferred that the heterocyclic compound has methyl, Ethyl, amino, the substituent group of one or more of nitro, further preferred meta position and/or contraposition replace.
3. catalyst according to claim 1, it is characterised in that: 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)OxIn one Kind or two kinds or more；
The MnOx、ZnOx、CeOx、GaOx、BiOx、InOxSpecific surface area be 1-100m2/g；It is preferred that specific surface area is 50- 100m2/g；
The MnaCr(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)OxRatio table Area is 5-150m2/g.It is preferred that specific surface area is 50-150m2/g；
The value range of the x is that the value range of 0.7~3.7, a is 0~1；The value range of a+b is 0~1.
4. catalyst described in accordance with the claim 1, it is characterised in that: the weight ratio of active ingredient and compositionⅱ in components I For 0.1-20, preferably 0.3-8.
5. catalyst described in accordance with the claim 1, it is characterised in that: be also added with dispersing agent, the metal in the component I Oxide is scattered in dispersing agent, dispersing agent Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3, active carbon, graphene, carbon receives One of mitron or two kinds or more.
6. catalyst described in accordance with the claim 1, it is characterised in that: in the components I, the content of dispersing agent is in 0.05- 90wt%, remaining is metal 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 the highly selective ethylene processed of synthesis gas reaction, it is characterised in that: using synthesis gas gaseous mixture as reaction raw materials, Conversion reaction is carried out in fixed bed or moving bed, obtains the low-carbon alkene product based on ethylene, and used catalyst is power Benefit requires any catalyst of 1-7.
9. according to the method described in claim 8, it is characterized by: the pressure of the synthesis gas is 0.5-10MPa, preferably 1- 8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 350-450 DEG C；Air speed is 300-10000h-1, excellent It is selected as 500-9000h-1, more preferably 500-6000h-1.The synthesis gas is to contain H2/ CO gaseous mixture, H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5；CO can also be contained in the synthesis gas2, wherein CO2Volumetric concentration in synthesis gas is 0.1-50%.
10. according to the method for claim 8, it is characterised in that: the method directly converts C processed with one-step method from syngas2-4 Alkene, ethylene selectivity 75-85%, byproduct methane selectivity < 5%.
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