CN108568311A - A kind of method of catalyst and synthesis gas directly conversion ethylene processed - Google Patents
A kind of method of catalyst and synthesis gas directly conversion ethylene processed Download PDFInfo
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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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Abstract
The invention belongs to synthesis gas directly to prepare ethylene, more particularly to a kind of method of catalyst and synthesis gas directly conversion ethylene processed, it is using synthesis 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 MOR structures；The weight ratio between active ingredient and B component in component A is between 0.1 20 ranges, and preferably 0.3 8.There is reaction process very high product yield and selectivity, the selectivity of low-carbon alkene can reach 80 90%, and wherein ethylene space-time yield is high, selectively reach 75 80%, at the same byproduct methane it is selectively extremely low (<15%), there is good application prospect.
Description
Technical field
The invention belongs to preparing low-carbon olefins, and in particular to a kind of catalyst and synthesis gas convert the side of ethylene processed
Method.
Background technology
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 as the low-carbon alkene of representative using ethylene, propylene, 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 oil.It converts coal, recyclable materials etc. to synthesis gas, then is given birth to by one step of raw material of synthesis gas
It produces the route of alkene and provides an alternative solution for naphtha pyrolysis technology production ethylene.One-step method from syngas is directly produced low
Carbon olefin be exactly carbon monoxide and hydrogen under the action of catalyst, carbon atom number is directly made by Fischer-Tropsch synthesis and is less than or waits
In the process of 4 low-carbon alkene, which is not necessarily to further make from synthesis gas through methanol or dimethyl ether as indirect method technique
Standby alkene, simplification of flowsheet greatly reduce investment.
Synthesis gas is always the research hotspot that synthesis gas directly produces alkene by the direct preparing low-carbon olefins of F- T synthesis
One of.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIAs alkali metal oxide such as MgO
Or iron-Mn catalyst system that silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite) supports, auxiliary agent is made with highly basic K or Cs ion, is being closed
It is 1.0~5.0MPa at gas reaction for preparing light olefins pressure, at 300~400 DEG C of reaction temperature, can get higher activity (CO
Conversion ratio 90%) and selectivity (selectivity of light olefin 66%).The patent ZL03109585.2 that Beijing University of Chemical Technology is declared
In, it uses vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. and is used for synthesis of gas produced low-carbon alkene for the Fe/ activated-carbon catalysts of auxiliary agent
Hydrocarbon reaction, under conditions of no unstripped gas recycles, CO conversion ratios 96%, selectivity of the low-carbon alkene in hydrocarbon
68%.The catalyst of above-mentioned report is to use metallic iron or cementite for active component, and the chain that reaction follows metal surface increases
The selectivity of long reaction mechanism, product low-carbon alkene is relatively low, and especially the selectivity of single product such as ethylene is less than 30%.2016
Year, Shanghai Institute for Advanced Study Sun Yuhan researcher and Zhong Liangshu researcher report a kind of preferentially exposure [101] and [020] manganese and help
Be carbonized cobalt-base catalyst, realizes under 31.8% CO conversion ratios, 60.8% selectivity of light olefin, and methane selectively
5%.But ethylene single selective is but less than 20%.Dalian Inst of Chemicophysics, Chinese Academy of Sciences's packet letter and academician and Pan Xiu
Lotus researcher reports the ZnCr of alumina load2O4Oxide and the compound bifunctional catalyst of multi-stage porous SAPO-34 molecular sieves
(351 (2016) 1065-1068 of Jiao et al., Science), when realizing CO conversion ratios 17%, low-carbon alkene 80%
Selectivity, but the selectivity of ethylene is less than 30%.In the patent 201610600945.6 that they apply, using containing oxygen vacancies
It is used for one step olefine reaction of synthesis gas with the compound bifunctional catalyst of MOR molecular sieves, the selectivity of ethylene is improved to 30-
75%, but in by-product carbon atom number be more than 3 hydro carbons it is more, affect the application of the technology.
Invention content
The technology of the present invention solves the problems, such as：It overcomes the deficiencies of the prior art and provide a kind of catalyst and synthesis gas directly converts
The method of ethylene processed, the catalyst invented can catalyze and synthesize gas and directly be converted into low-carbon alkene, and single product ethylene
Selectivity may be up to 75-80%.
The technical scheme is that：A kind of catalyst is combined with each other by component A and B component in a manner of mechanical mixture,
The active ingredient of component A is metal oxide, and B component is the molecular sieve of MOR topological structures, it is characterised in that：In B component, institute
It is 0.01mmol/g-0.6mmol/g to state B acid contents in the 8 membered ring cage of molecular sieve of MOR topological structures.
B acid contents preferred 0.1-0.6mmol/g, more preferable 0.25- in the 8 membered ring cage of molecular sieve of the MOR topological structures
0.6mmol/g.The B acid is Bronsted acid in framework of molecular sieve, and feature and content can be by infrared spectrum or nuclear magnetic resonance sides
Method determines.B acid position corresponds to different vibrational wave number ranges (according to document N.Cherkasov in infrared spectrum in different ducts
et al./Vibrational Spectroscopy 83(2016)170–179)。
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；
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 the reasonable 80%-10% by stoichiometric ratio oxygen molar content of oxygen atom mole, more preferably 60-
10%, most preferably 50-10%；Surface Lacking oxygen is defined as that (1- oxygen atom moles are 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%.
Dispersant, dispersant Al are also added in component A2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3In one kind or
Two kinds, metal oxide dispersion is in dispersant, and content of the dispersant in component A is in 0.05-90wt%, preferably 0.05-
25wt%, remaining is metal oxide.
The MOR topological structures are a kind of rhombic systems, have the one-dimensional channels for the oval straight channels being mutually parallel
Structure contains 8 annulus pockets and 12 annulus one-dimensional channels；[ATLAS OF ZEOLIE FRAMEWORK TYPES,
Ch.Baerlocher et.al.,2007,Elsevier.]。
The backbone element composition of the molecular sieve with MOR topological structures can be Si-Al-O, Ga-Si-O, Ga-Si-
One or two or more kinds in Al-O, Ti-Si-O, Ti-Al-Si-O, Ca-Al-O, Ca-Si-Al-O.
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 or two or more kinds in He and Ar, 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 of B acid is in the more 8 annulus cages of acquisition：Multiple nitric acid ammonium chloride carries out ion exchange to MOR, ensures
Alkali metal ion in 8 annulus cages is completely converted into B acid, additionally by first selectively occupying 12 annulus ducts using appropriate pyridine
Position reuses aluminum nitrate, to carrying out mending aluminium processing in 8 annulus cages, obtains more B acid position.
The mechanical mixture can be used mechanical agitation, ball milling, shaking table mixing, in mechanical lapping it is one or two or more kinds of into
Row is compound.
A kind of method that synthesis gas directly converts ethylene processed, is related to using synthesis gas as reaction raw materials, in fixed bed or movement
Conversion reaction is carried out on bed, used catalyst 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。
The reaction synthesis gas H2/ CO molar ratios are 0.2-3.5, preferably 0.3-2.5.
The dual-function composite catalyst is for one-step method from syngas directly conversion ethylene processed or the low-carbon alkene of C2-C4
Hydrocarbon, wherein ethylene selectivity reach 75-80%, with also when byproduct methane it is selectively low (<15%).
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 75-80%, and space-time yield is high, product is easy
In separation, there is good application prospect.
(3) catalyst of the present invention and patent application 201610600945.6 above-mentioned the difference is that, present invention catalysis
B acid contents are 0.01mmol/g-0.6mmol/g in the 8 membered ring cages of component B in agent, catalyze and synthesize gas and convert to obtain single component
The high selectivity of ethylene reaches 75-80%, and catalyst cannot meet the condition in aforementioned 201610600945.6, therefore it is catalyzed
Reaction result is that product is wider, and ethylene selectivity is less than 75%.
Specific implementation mode
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 be not meant to must satisfy these
Condition can just reach this purpose.
Embodiment 1
One, the preparation of component A
(1) ZnO material of the etching method synthesis with 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 waters that measure are added in 4 containers, and stirring 0.5h or more makes solution be uniformly mixed.Heating
It it is 160 DEG C, reaction time 20h to temperature, precipitation resolves into zinc oxide；Cooled to room temperature.Reaction solution, which centrifuges, to be received
2 acquisition ZnO oxides are washed with deionized in sediment after collection centrifugation；
The product of wherein 0.480g (12mmol) NaOH dosages is taken to carry out following processing：
(2) etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrate are used, it is super with ZnO oxides at normal temperatures
Sound mixing, ZnO oxides are soaked in etchant solution, and etching agent forms complexing or direct reduction reactor with zinc oxide；
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
The mass ratio of agent, oleic acid -5wt% hydrazine hydrates is 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 or two or more kinds in Ar, 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 (the reasonable opinion stoichiometric ratio oxygen molar content of 1- oxygen atom moles).
The preparation of 1 ZnO material of table and its performance parameters
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 metal that Zn is restored completely
Zn 5；
(2), MnO material of the etching method synthesis with polar surfaces：Preparation process corresponds to (1) in above-mentioned (one)
The product of 0.480g (12mmol) NaOH dosages and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Mn
Presoma, can be manganese nitrate, manganese chloride, one kind in 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) CeO of the etching method synthesis with polar surfaces2Material：Preparation process corresponds to (1) in above-mentioned (one)
The product of 0.480g (12mmol) NaOH dosages and (3) are described, the difference is that the presoma of Zn to have been changed into the correspondence of Ce
Presoma, can be cerous nitrate, cerium chloride, one kind in 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) nanometer Zn Cr of the synthesis with 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, the solid of gained is roasted, obtained in air atmosphere
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 moles are reasonable
By stoichiometric ratio oxygen molar content).
The preparation of 2 spinel of table and its performance parameter
(5) nanometer Fe Al of the synthesis with 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 kind in a kind of or cobalt nitrate, cobalt chloride, cobalt acetate in sour iron, iron chloride, ironic citrate, is 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, precipitation sedimentation prepares Cr2O3、Al2O3Or ZrO2The metal of dispersion aoxidizes
Object.For disperseing the preparation of ZnO oxides, 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 oxides.
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 dispersant 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 oxides of support dispersion, (dispersant 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 structures)
The MOR topological structures are a kind of rhombic systems, have the one-dimensional channels for the oval straight channels being mutually parallel
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, Ludox 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, wash afterwards for 24 hours, dry to get to modenite sample
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, obtains h-mordenite.
The molecular sieve that will be prepared handles 2h in the pyridine adsorption of 100Torr, 1h is handled in 100 DEG C in inert gas
Afterwards, using aluminum nitrate solution (concentration：1M), 8h, 60 DEG C of stirring 2h, rear centrifugation 1 time, 380 DEG C of skies after 140 DEG C of drying are stirred at room temperature
Gas roasts 1h.Reuse 1M ammonium nitrate solutions, 80 DEG C of stirring 3h.Centrifuge washing.140 DEG C of drying afterwards.In above-mentioned process, also may be used
To use titanium sulfate or gallium nitrate to replace aluminum nitrate.
By the above process prepare the molecular sieve with MOR topological structures backbone element form can be Si-Al-O,
One kind in 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 elements of part skeleton, corresponding product is defined as MOR1-8 successively；
Table 3 has preparation and its performance parameter of the molecular sieve of MOR topological structures
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, 20-100 DEG C of mixing temperature can be set, 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 5~50%, c) CO and nitrogen and/or the gaseous mixture of inert gas, bodies of the wherein CO in gaseous mixture
Product is 5~20%, d) O2With nitrogen and/or the gaseous mixture of inert gas, wherein O2Volume in gaseous mixture is 5-20%, institute
It is one or more of helium, argon gas, neon to state inert gas.
Mechanical agitation：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), can adjust the mixability and relative distance of component A and B component.
Ball milling：It is rolled at a high speed in grinding pot with catalyst using abrasive material, intense impact is generated to catalyst, is rolled, is reached
To dispersion, the effect of mixing component A and B component.By controlling 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), can adjust catalyst granularity 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 6.
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 gauge, online product analysis chromatography
Analysis).
The catalyst 2g of aforementioned present invention is placed in fixed bed reactors, using the air in Ar metathesis reactors, so
Afterwards again in H2300 DEG C are warming up in atmosphere, switching and merging gas (H2/ CO molar ratios=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.Low-carbon alkene (one kind of ethylene, propylene butylene or two
Kind or more) selectivity in the product is up to 80~90%, feed stock conversion 10-60%；Due to catalyst metals compound table
Face hydrogenation activity is not high, avoids a large amount of generations of methane, and methane selectively is low, and the selectivity of wherein ethylene reaches 75-80%.
The application of 5 catalyst of table and its effect
The catalyst that comparative example 3 uses is component A metal ZnCo+MOR3, ZnCo molar ratio 1：1, ZnCo with point 1 mass ratio
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+ MOR3, remaining parameter and mixed process etc. are same to urge
Agent C.
Molecular sieve is the commodity SAPO-34 purchased from Catalyst Factory, Nankai Univ in the catalyst that comparative example 5 uses.
Molecular sieve is the commodity ZSM-5 purchased from Catalyst Factory, Nankai Univ, full micropore knot in the catalyst that comparative example 6 uses
Structure, Si/Al=30.
The reaction result of comparative example 5 and 6 shows that the topological structure of MOR is most important to the modulation of selectivity of product,
The pore structure of SAPO34 mainly generates that C3 products are more, and ethylene selectivity is not high, and ZSM5 pore structures are suitble to generate C4 hydro carbons very
To the hydro carbons of more Long carbon chain.In contrast, 8 ring structures of MOR are more suitable for main product ethylene, have other structures molecular sieve institute not
Have the advantage that characteristic.
The content in the acid sites LF class B in 8 membered rings of MOR molecular sieves significantly affects the selection of ethylene as can be seen from the above table
Property.The ethylene selectivity that corresponding catalyst result of implementation C, D, J, K, Q, R, S, T, Z4, Z5, Z7, Z8, Z9 show advantage is timely
Empty yield, because they meet content sour in optimal oxygen vacancies and 8 membered ring cages simultaneously, and the two mass ratio meets the requirements.
Other samples cannot meet above-mentioned requirements simultaneously, so cannot get high space-time yield and selectivity, illustrate this difunctional
The content of two kinds of components and matching relationship are extremely important to performance in catalyst.
Above example is provided just for the sake of the description purpose of the present invention, and is not intended to limit the scope of the present 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 repaiies
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 groups
The active ingredient divided is metal oxide, and B component is the molecular sieve of MOR topological structures, it is characterised in that：It is described in B component
B acid contents in the molecular sieve octatomic ring cage of MOR topological structures are 0.01mmol/g-0.6mmol/g.
2. catalyst according to claim 1, it is characterised in that：B in the molecular sieve octatomic ring cage of the MOR topological structures
Acid content preferred 0.1-0.6mmol/g, more preferable 0.25-0.6mmol/g.
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、FeAl2O4In one kind or two kinds
More than；Preferably MnO, MnCr2O4、MnAl2O4、MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4In one kind or two kinds
More than；More preferably MnO, MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、FeAl2O4In one or two or more kinds.
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. according to claim 1-4 any one of them catalyst, it is characterised in that：The metal oxide from grain surface to
Intra-die direction depth be 0.3nm distance range in, surface Lacking oxygen be 20% or more, preferably 20-90%, more preferably
For 40-90%, most preferably 50-90%.
6. according to claim 1-4 any one of them catalyst, it is characterised in that：Dispersant is also added in the component A,
Dispersant is Al2O3、SiO2、Cr2O3、ZrO2、TiO2、Ga2O3In one or two or more kinds, metal oxide dispersion is in dispersion
In agent, for content of the dispersant in component A in 0.05-90wt%, preferably 0.05-25wt%, remaining is metal oxide.
7. according to claim 1-4 any one of them catalyst, it is characterised in that：The bone of the MOR topological structures 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
In one or two or more kinds.
8. a kind of method of synthesis gas directly conversion ethylene processed, it is characterised in that：Using synthesis gas as reaction raw materials, in fixed bed or
Conversion reaction is carried out on moving bed, used catalyst is any catalyst of claim 1-7.
9. according to the method described in claim 8, it is characterized in that：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 300-450 DEG C；Air speed is 300-10000h-1, excellent
It is selected as 500-9000h-1, more preferably 500-6000h-1。
10. according to the method described in claim 8, it is characterized in that：The synthesis gas is H2/ CO gaseous mixtures, H2/ CO molar ratios
For 0.2-3.5, preferably 0.3-2.5.
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| CN111346665A (en) * | 2018-12-21 | 2020-06-30 | 中国科学院大连化学物理研究所 | MOR-based bifunctional catalyst and method for preparing ethylene by directly converting synthesis gas |
| CN111760586A (en) * | 2019-04-02 | 2020-10-13 | 中国科学院大连化学物理研究所 | LF type B acid catalyst containing heteroatom and method for preparing ethylene by directly converting synthesis gas |
| CN112191278A (en) * | 2020-10-27 | 2021-01-08 | 正大能源材料(大连)有限公司 | Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
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