CN108970637A - A kind of method that catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins - Google Patents
A kind of method that catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins 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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- 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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- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to synthesis gas liquid fuel was prepared co-producing light olefins, and in particular to a kind of method that catalyst and synthesis gas directly convert preparing liquid fuel co-producing light olefins.It using synthesis gas as reaction raw materials, is reacted in fixed bed or moving bed, the catalyst contains A and B component, and component A is reactive metal oxides, and component B activity group is divided into the molecular sieve with CDO structure；The weight ratio of catalyst A and catalyst B is 0.1-20.Synthesis atmospheric pressure is 0.1-10MPa, and reaction temperature is 300-600 DEG C, air speed 300-20000h‑1.The high gasoline of main product octane number, co-production low-carbon alkene are reacted, while byproduct methane is selectively low (< 10%), has a good application prospect.
Description
Technical field
The invention belongs to synthesis gas liquid fuel was prepared co-producing light olefins, and in particular to a kind of catalyst and synthesis gas are straight
The method of switching through preparing liquid fuel co-producing light olefins.
Background technique
With economic development and improvement of living standards, the demand of liquid fuel and chemicals also year by year sharply on
It rises.Gasoline production is mainly obtained by the catalytic reforming of heavy naphtha at present.As Global Oil resource increasingly consumes and occupies height not
Under crude oil price, especially for China of petroleum resources scarcity, per year over nearly 60% consumption of petroleum amount rely on import,
Seek a kind of process route that can be substituted, development and utilization are prepared the side of low-carbon alkene by the non-oil base carbon resource such as coal, biomass
Method has important social effect and strategic importance.
Rich coal resources in China obtains synthesis gas (i.e. the gaseous mixture of CO and H2) using coal as raw material by gasification, will
Synthesis gas is converted to methanol, and the brief introduction technology path that methanol produces gasoline through dimethyl ether again is mature, and steps into industrialization, should
The carbon resources preparing liquid fuels such as route is coal, natural gas provide an important variation route.However, straight if being able to achieve synthesis gas
Switching through, and without the direct route of methanol-fueled CLC and preparing dimethyl ether by dewatering methanol, it not only can simplify process flow, but also
Unit operation can be reduced, investment and energy consumption are reduced.Traditional Fischer-Tropsch path may be implemented synthesis gas directly conversion and prepare liquid
Fuel, however limited by its reaction mechanism, CO and H2In catalyst surface Dissociative occurs for molecule, generates surface C atom
And O atom, C atom and O atom react with the hydrogen for being adsorbed on catalyst surface, form methylene (CH2) intermediate, simultaneously
Release hydrone.Methylene intermediate carries out free crowd by migration intercalation reaction, in catalyst surface, generates and contains different carbon
The hydrocarbon product of atomicity (ten from one to three, even arriving a carbon atoms up to a hundred sometimes).Entire reaction hydrocarbon product carbon atom number
Distribution is wide, and the selectivity of target product is low, as the selectivity of gasoline is lower than 50%.
Low-carbon alkene (Light Olefins) includes mainly ethylene, propylene and butylene, is the foundation stone of modern chemical industry,
Low-carbon alkene is mainly prepared by naphtha pyrolysis at present.Synthesis gas is obtained by coal gasification, is then converted into methanol or dimethyl ether,
Methanol or dimethyl ether are then converted into the technology relative maturity of the multiple reactors of multistep of low-carbon alkene, have been carried out industry
Change.In order to simplify reaction process, shorten process route, people to based on traditional Fischer-Tropsch reaction catalyst, as Fe base catalyst into
Row modification and improvement, add the additive of different compositions, such as alkali metal K, Na and transient metal Mn, Cu, can be effectively improved
The selectivity of low-carbon alkene.German Rule chemical company develops the Fe-Zn-Mn-K catalyst of multicomponent auxiliary agent promotion, is used for
The synthesis [12] of low-carbon alkene.The report such as Beijing University of Chemical Technology Zhang Jingchang is urged by the Fe-Mn-K/AC of precursor preparation of ferric oxalate
Agent is in air speed 600h-1, at 15bar and 320 DEG C, the high conversion rate of CO is up to 97%, C2 =-C4 =Selection in hydrocarbon
Property for 68% [Zhang Jingchang, defend the country guest, Cao Weiliang, is catalyzed journal 24 (2003) 259-264], be more than pre- by ASF distributed model
The C of survey2-C4The selectivity of hydrocarbon.The carrier of catalyst also plays the selectivity of product important by the interaction with Fe species
Modification.Dutch de Jong seminar is reported recently with carbon nano-fiber (CNF) and α-Al2O3For carrier, with citric acid
Sideramines is the 12wt%Fe catalyst of precursor preparation, at low pressure (1bar), 350 DEG C, and H2Under the conditions of/CO=1, reaction 15 is small
When, CO conversion ratio be 0.5-1.0%, selectivity of the low-carbon alkene in hydrocarbon be 60% [H.M.T.Galvis,
J.H.Bitter,C.B.Hhare,M.Ruitenbeek,A.L.Dugulan,K.P.de Jong,Science 335(2012)
835-838].Same catalyst existsH2/ CO=1,20bar, air speed 1500h-1Under, obtain the conversion of 70-88%
Rate, FTY are respectively 2.98 × 10-5Mol CO/gFes and 1.35 × 10-5Mol CO/gFes, CO2Selectivity be 42-
46%, wherein selectivity of the low-carbon alkene in hydrocarbon is 52-53%.Then they have found, micro in catalyst
0.03%S, 0.2% or so Na have apparent facilitation to the selectivity of reactivity and low-carbon alkene
[H.M.T.Galvis,A.C.J.Koeken,J.H.Bitter,T.Davidian,M.Ruitenbeek,A.I.Dugulan,
K.P.de Jong,J.Catal.303(2013)22-30].The Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences has made system to absorbent charcoal carrier
In-depth study finds that product deviates ASF distribution [Shen Jianyi, Lin Liwu, Zhang Su, Liang Dong on activated carbon supported iron catalyst
It is white, chemistry of fuel journal 19 (1991) 289-297；Marvin's is flat, Ding Yunjie, Luo Hongyuan etc., is catalyzed journal 22 (2001) 279-
282].In addition, the preparation method and technique of catalyst, such as roasting process, reducing condition, active component can be directly affected
Dispersion and size, thus the selectivity of the activity of modulation reaction and product.Beijing University of Chemical Technology combines skill using supercritical fluid
Art (i.e. chemical precipitation, gellike, supercritical drying method) make active component Fe and auxiliary agent high degree of dispersion, be prepared for nanoscale
Fe base catalyst, the conversion ratio of CO are greater than 96%, and selectivity of the low-carbon alkene in hydrocarbon is greater than 54% [Beijing chemical industry
University, a kind of nanocatalyst and preparation method for preparation of low carbon olefines by synthetic gas: China, 101396662 [P] .2009-
04-01]。
For this purpose, also there is researcher to try the coupling of multiple processes, and a large amount of trial is carried out.Xu etc. is by CuO-
ZnO-Al2O3 is mixed with ZSM-5, obtained catalyst, and the product obtained in synthesis syngas conversion reactor is mainly dimethyl ether
[M.Xu,J.H.Lunsford,D.W.Goodman,A.Bhattacharyya,Appl.Catal.A.General 149(1997)
289；D.Mao,W.Yang,J.Xia,B.Zhang,Q.Song,Q.Chen,J.Catal.230(2005)140].Erena etc. will
The multicomponents metal composite such as CuO/ZnO/Al2O3 is mixed with ZSM-5 molecular sieve, catalyzes and synthesizes gas conversion, obtained product master
It to be gasoline [J.Erena, J.M.Arandes, J.Bilbao, A.G.Gayubo, H.I.De Lasa, Chemical
Engineering Science 2000,55,1845；J.Erena,J.M.Arandes,R.Garona,A.G.Gayubo,
J.Bilbao,Journal of Chemical Technology and Biotechnology 2003,78,161].Park etc.
By dual bed reactor, 300 DEG C, 10atm, GHSV=3600h first on first reactor Fe-Cu-Al catalyst-1Under
Fischer-Tropsch reaction is carried out, using ZSM-5 catalyst for cracking bed at second 500 DEG C of reactor, by a large amount of C5+Product cracking
For low-carbon alkene, the selectivity of lower carbon number hydrocarbons is 52% in thus obtained hydrocarbon, and low-carbon alkene is in output aggregate
Selectivity be 28% [J.L.Park, Y.J.Lee, K.W.Jun, J.W.Bae, N.Viswanadham, Y.H.Kim,
J.Ind.Eng.Chem.15(2009)847-853]。
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of catalyst and synthesis gas directly to convert preparing liquid fuel coproduction low-carbon
The method of alkene, the catalyst invented can catalyze and synthesize gas and directly be converted into liquid fuel co-producing light olefins, and gasoline evaporates
Component selections can achieve 50-80%.
The technical solution of the present invention is as follows:
A kind of catalyst, the catalyst are composite catalyst A+B, and the active ingredient of component A is reactive metal oxides,
Component B is the molecular sieve with CDO structure；Reactive metal oxides are MnO, MnCr2O4、MnAl2O4、MnZrO4、ZnO、
ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more.
Catalytic component A is preferably MnO, Cr2O3、MnCr2O4、MnAl2O4,MnZrO4、ZnAl2O4、CeO2、CoAl2O4、
FeAl2O4One of or two kinds or more；More preferably MnO, Cr2O3、MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、
FeAl2O4One of or two kinds or more；
The molecular sieve of CDO structure is made of H, O, Si, Al in catalytic component B；Al2O3, stone can also be contained in component B
Ink, SiO2, ZrO2, TiO2, Cr2O3, Ga2O3, CaO, MgO, CeO2, one or more kinds of dispersion in In2O3, SnO2
Agent, dispersant are 0-50%wt.Spacing between the geometric center of the particle of the reactive metal oxides and component B of component A
Between 20nm-10mm, preferably 50nm-1mm, more preferably 100nm-0.5mm.
Weight ratio between active ingredient in component A and component B is between 0.1-20 times of range, preferably 0.3-5.
Reactive metal oxides are made of the crystal grain that size is 5-30nm, are from grain surface to intra-die direction depth
It than oxygen molar content is in terms of 100% by theoretical stoichiometric, Surface Oxygen is empty there are a large amount of oxygen vacancies in the distance range of 0.3nm
Position percentage concentration is defined as (the reasonable percentage by stoichiometric ratio oxygen molar content of 100%- oxygen atom mole), Lacking oxygen
Concentration is preferably 20-90%, more preferably 40-90%, most preferably 50-90%.
Dispersing agent, dispersing agent Al are also added in the catalyst A2O3、Cr2O3、ZrO2、TiO2One of or two
Kind, reactive metal oxides are scattered in dispersing agent, and for content of the dispersing agent in catalyst A in 10-90wt%, remaining is activity
Metal oxide.
A kind of method that synthesis gas directly converts preparing liquid fuel co-producing light olefins, using synthesis gas as reaction raw materials,
Conversion reaction is carried out in fixed bed or moving bed.
The pressure of the synthesis gas is 0.1-10MPa, preferably 1-8MPa, more preferably 2-8MPa；Reaction temperature is
300-600 DEG C, preferably 300-500 DEG C；Air speed is 300-20000h-1。
Reaction is H with synthesis gas2/ CO mixture, can also contain other gases；Other gases include CO2, N2, Ar, He, first
Alkane, ethane, ethylene；Other gas contents are 0.1-10%；Wherein H2/ CO ratio is 0.2-3.5, preferably 0.3-2.5.
The liquid fuel is mainly gasoline, and based on high-octane isomery hydro carbons, while co-producing light olefins, low
Carbon olefin refers to one of alkene of the C2-C4 containing 2 to 4 carbon atom numbers, including ethylene, propylene, butylene or two kinds or more.
The present invention has the advantage that
1. this technology is different from traditional technique for preparing gasoline by methanol (referred to as MTG), a step is realized directly for synthesis gas
Convert preparing liquid fuel and low-carbon alkene.
2. gasoline fraction selectivity is high in product, 50-80% can reach, and be mainly high added value in remaining product
Low-carbon alkene, selectivity of light olefin can reach 10-30%.
3. compared to traditional F- T synthesis technology, in gasoline composition based on high-octane isomery hydro carbons, straight-chain hydrocarbons
Class is selectively low, and oil quality is high；And byproduct methane is selectively low, is lower than 10%.
4. the preparation process simple condition of the composite catalyst in patent is mild；And reaction process is received with very high product
Rate and selectivity, have a good application prospect.
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 catalyst A
(1), etching method synthesis has the ZnO material of polar surfaces:
(1) 0.446g (1.5mmol) Zn (NO is weighed3)2·6H2O and 0.480g (12mmol) NaOH, then measure 30ml and go
Ionized water is added thereto, and stirring 0.5h or more is uniformly mixed solution.Being warming up to temperature is 160 DEG C, reaction time 20h, is sunk
Resolve into zinc oxide in shallow lake；Cooled to room temperature.The sediment after centrifuge separation is collected in reaction solution centrifuge separation, uses deionized water
Wash 2 acquisition ZnO oxides；
(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；It will be upper
Suspended matter heating is stated, washing filtering is then taken out, obtains the nano ZnO material with exhibiting high surface oxygen vacancies.
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, not molten
The mass ratio of agent, oleic acid -5wt% hydrazine hydrate 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 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 dense
Degree is defined as (100%- 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, ZnO 9 of the surface without Lacking oxygen without (2) step etching, and the gold that Zn is restored completely
Belong to Zn 10；
(2), etching method synthesis have polar surfaces MnO material: preparation process with above-mentioned (one), the difference is that
The presoma of Zn has been changed into the corresponding presoma of Mn, has been one of manganese nitrate, manganese chloride, manganese acetate.
Etch processes are with described in the product ZnO 3, ZnO 5 of (2) in above-mentioned (one), 8 preparation process of ZnO, synthesis tool
There is the catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 56%, 36%, 27%；
Corresponding product is defined as MnO 1-3；
(3), etching method synthesis has the CeO of polar surfaces2Material: preparation process with above-mentioned (one), the difference is that
The presoma of Zn has been changed into the corresponding presoma of Ce, has been one of cerous nitrate, cerium chloride, cerous acetate.
Described in product ZnO3, ZnO4, ZnO8 preparation process of the etch processes with (2) in above-mentioned (one), synthesis has
The catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 67%, 38%, 25%；
Corresponding product is defined as CeO 1-3；
(4), etching method synthesis has the Cr of polar surfaces2O3Material:
Preparation process the difference is that the presoma of Zn to have been changed into the corresponding presoma of Cr, is with above-mentioned (one)
One of chromic nitrate, chromium chloride, chromic acetate.
Described in product ZnO3, ZnO4, ZnO8 preparation process of the etch processes with (2) in above-mentioned (one), synthesis has
The catalyst of exhibiting high surface Lacking oxygen；Surface Lacking oxygen 45%, 29%, 20%；
Corresponding product is defined as Cr2O31-3；
(5), 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, are nitric acid the difference is that the presoma of Zn to have been changed into the corresponding presoma of Fe or Co
One of iron, iron chloride, ironic citrate or one of cobalt nitrate, cobalt chloride, cobalt acetate.
With described in the product ZnO 3 of (2) in above-mentioned (one), 5 preparation process of ZnO, synthesis has a large amount of etch processes
The catalyst of surface Lacking oxygen；Surface Lacking oxygen 77%, 51%；
Corresponding product is defined as spinelle 6, spinelle 7；
(6), Cr2O3、Al2O3Or ZrO2The reactive metal oxides of dispersion
With Cr2O3、Al2O3Or ZrO2For carrier, precipitates sedimentation and prepare Cr2O3、Al2O3Or ZrO2The active metal of dispersion
Oxide.For dispersing the preparation of ZnO oxide, by business Cr2O3、Al2O3Or ZrO2Carrier is scattered in advance in the liquid of bottom, so
Use zinc nitrate for raw material afterwards, with sodium hydroxide pellets agent mixed precipitation at room temperature, Zn2+Molar concentration be 0.067M, Zn2 +Molfraction ratio with precipitating reagent is 1:8；Then it is aged 24 hours at 160 DEG C, obtains Cr2O3、Al2O3Or ZrO2For carrier
The ZnO oxide of dispersion (content of the dispersing agent in catalyst A is followed successively by 0.1wt%, 10wt%, 90wt%).
With described in the product ZnO 3, ZnO 5 of (2) in above-mentioned (one), 8 preparation process of ZnO, synthesis has big etching process
The catalyst of scale face Lacking oxygen；Surface Lacking oxygen 65%, 30%, 25%；Last handling process is in above-mentioned (one) 3) it is described；
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 5wt%, 30wt%, 60wt%), surface Lacking oxygen 62%, 27%, 28%；It corresponds to from top to bottom
Product is defined as dispersal oxide 4-6.
Two, the molecular sieve with CDO topological structure, the i.e. preparation of component B:
1) specific preparation process are as follows:
It is described: the preparation method reference literature of CDO molecular sieve:
Angew.Chem.Int.Ed.2004,43,4892-4896；Chem.Mater.2013,25,840-847；
J.Mater.Chem.,2011,21,9494；
White carbon black: 10g, TMAOH, 22g, 15wt%, KOH 5g, Isosorbide-5-Nitrae-dioxane 50g sequence are added in 25g water.It stirs
1h is mixed, later in 300ml kettle, 423K crystallization 10 days.70 DEG C of dry 12h after centrifuge washing later.823K is heated in vacuum,
The molecular sieve of CDO structure is obtained after 4h.
Three, the preparation of catalyst
The component A of required ratio and component B 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
Carry out, atmosphere are as follows: a) nitrogen and/or inert gas, b) gaseous mixture of hydrogen and nitrogen and/or inert gas, 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, being mixed component A and B 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.
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 composition A and B.By control abrasive material, (material can be stainless steel, agate, quartz.Size range:
5mm-15mm).With the ratio (quality is than range: 20-100:1) of catalyst, the granularity and relative distance of adjustable catalyst.
Shaking table mixing method: component A and B are pre-mixed, and are fitted into container；By the reciprocating vibration or circumference that control shaking table
The mixing of component A and B are realized in oscillation；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 are pre-mixed, and are fitted into container；In certain pressure, (range: 5 kilogram -20 public
Jin) under, relative motion (speed range: 30-300 turns/min) is carried out with mixed catalyst by lap tool, reaches adjusting catalysis
Agent granularity, 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 5 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 of aforementioned present invention is placed in fixed bed reactors, using the air in Ar metathesis reactor, then
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.
1. changing temperature, pressure and air speed, thus it is possible to vary reactivity worth.Gasoline fraction selectivity is high in product, can reach
50-80%, and predominantly the low-carbon alkene of high added value, selectivity of light olefin can reach 10-30% in remaining product.
Synthetic technology is opened up compared to traditional expense, byproduct methane is selectively extremely low, is lower than 10%；And gasoline composition in
Based on high-octane isomery hydro carbons and aromatic hydrocarbons, straight chain hydrocarbon is selectively low, and oil quality is high.
The application of 6 catalyst of table and its effect
ZnO does not have oxygen vacancies in 1 catalyst of comparative example, therefore its activity is very low.
ZnO is reduced into metallic state completely in 2 catalyst of comparative example, causes the selectivity of methane in product very high.
For the catalyst that comparative example 3 uses for component A metal ZnCo, component B is CDO, ZnCo molar ratio 1:1, ZnCo and CDO
Mass ratio 1:1, remaining parameter and mixed process etc. are the same as catalyst A.
The catalyst component A that comparative example 4 the uses MgO for surface without oxygen vacancies, component B are CDO, remaining parameter and mixing
Process etc. is the same as catalyst A.
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 small pore molecular sieve of LEV structure in the catalyst that comparative example 6 uses.
The distance between metal oxide and molecular sieve is 30mm in the catalyst that comparative example 7 uses, remaining parameter and mixed
Conjunction process etc. is the same as catalyst A.
Metal oxide is located in molecular sieve pore passage in the catalyst that comparative example 8 uses, the two close contact, remaining parameter
Deng with catalyst A.
Comparative example 9 is using the iron catalyst of carbon nanotube confinement, and wherein iron load capacity is 10%, and wherein C5+ product is in carbon
Selectivity in hydrogen compound is 29%.
Reaction result explanation:
Illustrate one:
The reaction result of comparative example 5 and 6 shows that topological structure is most important to the modulation of selectivity of product, SAPO34 tool
There is port sizeFor three-dimensional open-framework, it is suitble to the generation of C2-C4 hydro carbons, wherein C3 hydrocarbon products are most；And LEV is also
8 member rings, port size areCage size ratio sapo34 is smaller, therefore methane is very high in product.
The CDO molecular sieve that this patent uses has 8 annulus apertures, and two-dimensional channel structure shows other structures molecular sieve
The advantages characteristic not had, product is mainly gasoline fraction, and the content of isoparaffin is high.Co-producing light olefins simultaneously.
Illustrate two:
The distance between metal oxide and molecular sieve is 30mm in the catalyst that comparative example 7 uses, remaining parameter and mixed
Conjunction process etc. is the same as catalyst A.
Metal oxide is located in molecular sieve pore passage in the catalyst that comparative example 8 uses, the two close contact, remaining parameter
Deng with catalyst A.
The reaction result of comparative example 7 and comparative example 8 shows apart from remote and too closely to result in methane selectively very high, and
It is unfavorable for the generation of gasoline fraction.
The structure of molecular sieve as can be seen from the above table, including between topological structure and metal oxide and molecular sieve
Distance matching is most important, directly affects the selectivity of gasoline fraction and low-carbon alkene.
The reaction result of comparative example 7 and comparative example 8 shows apart from remote and too closely to result in methane selectively very high, and
It is unfavorable for the generation of gasoline fraction.
The structure of molecular sieve as can be seen from the above table, topological structure and metal oxide and molecular sieve including CDO it
Between distance matching it is most important, directly affect the selectivity of gasoline fraction and low-carbon alkene.
Claims (9)
1. a kind of catalyst, it is characterised in that: the catalyst is composite catalyst A+B, and the active ingredient of component A is activity gold
Belong to oxide, component B is the molecular sieve with CDO structure；Reactive metal oxides are MnO, MnCr2O4、MnAl2O4、MnZrO4、
ZnO、ZnCr2O4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more.
2. catalyst described in accordance with the claim 1, it is characterised in that: catalytic component A is preferably MnO, Cr2O3、MnCr2O4、
MnAl2O4,MnZrO4、ZnAl2O4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more；More preferably MnO, Cr2O3、
MnCr2O4、MnAl2O4,MnZrO4、CeO2、CoAl2O4、FeAl2O4One of or two kinds or more.
3. catalyst described in accordance with the claim 1, it is characterised in that: in catalytic component B the molecular sieve of CDO structure by H, O,
Si, Al are constituted；It can also contain Al2O3 in component B, graphite, SiO2, ZrO2, TiO2, Cr2O3, Ga2O3, CaO, MgO,
One or more kinds of dispersing agent in CeO2, In2O3, SnO2, dispersant are 0-50%wt.
4. according to catalyst described in claim 1,2 or 3, it is characterised in that: between the active ingredient in component A and component B
Weight ratio between 0.1-20 times of range, preferably 0.3-5.
5. according to catalyst described in claim 1,3 or 4, it is characterised in that: reactive metal oxides are 5-30nm by size
Crystal grain constitute, from grain surface to intra-die direction depth in the distance range of 0.3nm, there are a large amount of oxygen vacancies, with
Theoretical stoichiometric is 100% meter than oxygen molar content, and surface Lacking oxygen percentage concentration is defined as (100%- oxygen atom mole
The reasonable percentage by stoichiometric ratio oxygen molar content), oxygen vacancy concentration is preferably 20-90%, more preferably 40-90%,
Most preferably 50-90%.
6. catalyst described in accordance with the claim 1, it is characterised in that: be also added with dispersing agent, dispersing agent in the catalyst A
For Al2O3、Cr2O3、ZrO2、TiO2One of or two kinds, reactive metal oxides are scattered in dispersing agent, and dispersing agent is in catalysis
For content in agent A in 10-90wt%, remaining is reactive metal oxides.
7. a kind of method that synthesis gas directly converts preparing liquid fuel co-producing light olefins, it is characterised in that: it is with synthesis gas
Reaction raw materials, carry out conversion reaction in fixed bed or moving bed, and used catalyst is claim 1-6 any described
Catalyst.
8. according to the method for claim 7, it is characterised in that: the pressure of the synthesis gas is 0.1-10MPa, preferably 1-
8MPa, more preferably 2-8MPa；Reaction temperature is 300-600 DEG C, preferably 300-500 DEG C；Air speed is 300-20000h-1。
9. according to method described in claim 7 or 8, it is characterised in that: the reaction is H with synthesis gas2/ CO mixture, may be used also
To contain other gases；Other gases include CO2, N2, Ar, He, methane, ethane, ethylene；Other volume concentration of gas phase are 0.1-
10%；Wherein H2/ CO ratio is 0.2-3.5, preferably 0.3-2.5.
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