CN104117380B

CN104117380B - The technique and used catalyst of synthesis gas conversion production hydrocarbon compound

Info

Publication number: CN104117380B
Application number: CN201310149855.6A
Authority: CN
Inventors: 葛庆杰; 王春; 马现刚; 徐恒泳
Original assignee: Dalian Institute of Chemical Physics of CAS; BP PLC
Current assignee: Dalian Institute of Chemical Physics of CAS; BP PLC
Priority date: 2013-04-26
Filing date: 2013-04-26
Publication date: 2019-05-14
Anticipated expiration: 2033-04-26
Also published as: CN104117380A

Abstract

The present invention relates to synthesis gas to convert production C₅₊The technique of saturated hydrocarbons, used dehydration/hydrogenation catalyst, and include dehydration/hydrogenation catalyst multistage catalyst system and composite catalyst.Wherein, the dehydration/hydrogenation catalyst includes solid acid substance or is made from it, which includes molecular sieve and/or metal modified molecular screen, wherein the silica alumina ratio of the molecular sieve and/or metal modified molecular screen is 100 or more.Technique through the invention, temperature is 200-400 DEG C, pressure is 5-40 bars, gas space velocity 500-20000h^‑1、H₂: under conditions of CO=0.5-2.5, synthesis gas can be converted into C in one or more snippets catalyst system_5‑11Saturated hydrocarbons.C in hydrocarbon product_5‑11Selectivity up to 69%, wherein C_5‑8The selectivity of isoparaffin is up to 77%, C in fraction_9‑11Fraction is then based on aromatic hydrocarbons.The present invention has opened up one and has produced C from non-oil resources such as coal, natural gas and biomass_5‑11The variation route of saturated hydrocarbons.

Description

The technique and used catalyst of synthesis gas conversion production hydrocarbon compound

Technical field

The present invention relates to the techniques that a kind of synthesis gas converts production hydrocarbon compound, more particularly to using one section or more Section catalyst system converts production C by synthesis gas₅And C₅The technique of above hydro carbons.

Background technique

In recent years, with the increasingly consumption of petroleum resources, with tar sand, coal, natural gas, biomass, urban waste etc. Non-oil resource is raw material, and the research for converting production hydrocarbon compound through synthesis gas is more and more important.

Early in the 1920s, just having developed the F- T synthesis work for converting production hydrocarbon compound by synthesis gas Skill.The active component of fischer-tropsch synthetic catalyst is mainly group VIII transition metals.It is demonstrated experimentally that with Fe, Co, Ni and Ru When equal metals are active component, C in Fischer-Tropsch product₅And C₅The yield of the above hydro carbons greatly improves.However with these traditional Fischer-Tropsch When synthetic catalyst, the distribution of product is limited by Anderson-Schulz-Flory (ASF) dynamic law.This distribution It is not high to the selectivity of product of midbarrel, such as gasoline fraction C_5-11Selectivity a maximum of about of 45%, diesel oil distillate C_12-20Selection Property highest only about 30%.

Recently, researcher proposes " modified FT synthesis " technique, wherein traditional fischer-tropsch synthetic catalyst is supported on It is mixed on acidic molecular sieve or with acidic molecular sieve, using the shape-selective effect of molecular sieve, effectively increases C in reaction product_5-12 The selectivity of hydro carbons.Document Jincan Kang etc., Angewandte Chemie International Edition, 2011, 50,5200-5203, report the ruthenium catalyst loaded with mesoporous ZSM-5 molecular sieve；Jun Bao etc., Applied Catalysis A:General, 2011,394,195-200, report Fe-ZSM-5 capsule catalyst all improves gasoline group in product Point selectivity, the selectivity of isoparaffin is also improved in gasoline component, and problem is byproduct methane and C_2-4Low-carbon alkanes Selectivity it is also very high.

In addition, the methanol synthesizing process of heavy industrialization, has pushed methanol selectivity catalyzed conversion to produce hydrocarbon The development of object technology, such as methanol-to-olefins (MTO), preparing gasoline by methanol (MTG) and methanol aromatic hydrocarbons (MTA).In these technique mistakes The methanol of Cheng Zhong, synthesis are separated with other components first, enter back into the stage of reaction of methanol conversion.

The present invention develops a kind of new technology of synthesis gas conversion production hydrocarbon compound.

Summary of the invention

The purpose of the present invention is develop a kind of new technology of synthesis gas conversion production hydrocarbon compound.The product of conversion is C₅₊ Fraction, wherein C_5-8Fraction is rich in isoparaffin, and C_9-11Fraction is mainly aromatic hydrocarbons.

Technical process of the present invention can be completed in single catalyst bed system.The catalyst bed can be by first Alcohol synthetic catalyst and metal-modified molecular sieve composition.

Technical process of the present invention can be completed in dual catalyst bed system.The catalysis of first catalyst bed Agent component can be methanol synthesis catalyst, and synthesis gas generates methanol on the first catalyst bed first；First catalyst bed The catalytic component of layer can be dimethyl ether synthetic catalyst, therefore diformazan can be generated on the first catalyst bed in synthesis gas Ether in some examples, can generate methanol and dimethyl ether simultaneously on the first catalyst bed.Therefore, in intermediate product stream It can simultaneously include methanol and/or dimethyl ether.The catalytic component of second catalyst bed is mainly dehydration catalyst.Some realities In example, the catalyst of the second catalyst bed is metal-modified.Second catalyst bed can have dehydration simultaneously and add hydrogen Activity.Aspect and feature according to the present invention according to circumstances can be applied to single catalyst bed system, also can be applied to The system of two sections of (double) catalyst beds or more catalyst bed.

The present invention attempts to provide by the new process of preparing hydrocarbon from synthetic gas compound.As shown in the Examples, product hydrocarbonaceous is outstanding It is C₅-C₈The selectivity of branched paraffin is very high in fraction, and arenes selectivity is lower.In certain embodiments, the present invention attempts to mention For the selectivity to heavy arene, especially C₉₊Aromatic hydrocarbons.

On the other hand, the present invention develops in multistage catalyst system, convert synthesis gas into the dehydrations of saturated hydrocarbons/ Hydrogenation catalyst, which includes molecular sieve or metal-modified molecular sieve, wherein the silica alumina ratio (SiO of the molecular sieve₂/ Al₂O₃Molar ratio) it is 50 or higher, preferably 100 or higher.

It is generally believed that the acidic zeolite position of high silica alumina ratio is fewer than the acidic zeolite position of low silica-alumina ratio, be conducive to improve The selectivity of isoparaffin in product hydrocarbon, and then be conducive to the generation of target product, such as improve C in product₅-C₈The branch of fraction The selectivity of alkane reduces the selectivity of alkene and aromatic hydrocarbons.

So the silica alumina ratio of molecular sieve can be 120 or more or 140 or more in second segment catalyst, divide in some examples The silica alumina ratio of son sieve is also possible to 200 or higher, 250 or higher, 300 or higher.In some examples, silica alumina ratio 360.

The silica alumina ratio of molecular sieve is significantly higher than conventional molecular sieve in second segment catalyst of the present invention, such as conventional molecular sieve Silica alumina ratio can be about 20.

The silica alumina ratio that specific molecular sieves sample can be measured by any suitable method, as ICP-MS(induces coupling Close plasma-mass spectrum) technology and XRF (X fluorescence spectrum analysis) technology etc..

Herein, when referring to dehydration/plus hydrogen, such as the catalyst for being dehydrated/adding hydrogen or group timesharing are referred to, it should Take the circumstances into consideration both to be interpreted as referring to dehydration plus hydrogen or dehydration and add hydrogen.

The catalyst can be prepared according to method for example as described in the examples described herein.Other methods can also be used Or other raw materials preparation.Therefore aspect of the present invention further includes that associated catalysts prepare raw material and method.In addition, this hair Bright some aspects further relate to above-mentioned catalyst, and no matter it uses which kind of raw material and method to prepare.

The molecular sieve catalyst can be one or more of for Y molecular sieve, beta-molecular sieve or ZSM-5 molecular sieve, preferably ZSM-5 molecular sieve.

Metal used in metal modified molecular screen can be Pd, Pt, Rh, Ru and/or Cu, preferably Pd and/or Cu.

The load capacity of metal is in about 0.1wt% between about 20wt%.The content of metal of some examples about 0.1wt% extremely Between about 2wt%, such as in about 0.5wt% between about 1wt%.

Dehydration/hydrogenation catalyst according to the present invention can be used in combination with other catalyst, as synthesis gas conversion is urged Agent.Therefore the present invention provides the catalyst systems comprising the dehydration/hydrogenation catalyst and syngas conversion catalyst.It should Catalyst system may include two-stage catalytic agent system, for example, in the system two sections of system be separation.The two-stage catalytic agent System can be a part of multistage catalyst system.In some instances, two kinds of catalyst may be mixed together, Huo Zheke With there are contact surfaces among stratiform filling, or two kinds of catalyst can also separately be loaded and be mutually not in contact with each other.Two catalyst Section can be separation.

Therefore another aspect of the present invention is to provide the multistage catalyst system for converting synthesis gas to saturated hydrocarbons.Catalyst System include comprising syngas conversion catalyst or the first segment catalyst that is made from it and comprising dehydration/hydrogenation catalyst or by Its second segment catalyst formed.Dehydration/the hydrogenation catalyst is comprising molecular sieve or metal-modified molecular sieve or by its group At wherein the silica alumina ratio of the molecular sieve is 50 or higher, preferably 100 or higher.

The multistage catalyst system can be it is independently divided open, can be segmentation connection, can be physical mixed , it is also possible to other filling modes.

Syngas conversion catalyst can be with methanol-fueled CLC activity and/or the active catalyst of DME synthesis.Example Such as, during two sections or multistage technology, first segment generates methanol or/and dimethyl ether.

It is limited by the process of synthesis gas synthesizing methanol by thermodynamical equilibrium.It is reported according to disclosed patent US3,326,956, Increasing pressure can be improved product yield, and improved catalyst can receive higher methanol at relatively low temperatures and generate Rate.Such as CuO/ZnO/Al₂O₃Methanol synthesis catalyst can operate at a temperature of 5-10MPa pressure and 150-300 DEG C.? It is operated under high temperature, the service life reduction of catalyst.Commercially available low pressure catalyst for synthesizing copper based methanol can be from BASF and Haldor- Topsoe purchase.When generally using catalyst for synthesizing copper based methanol, the yield of methanol can achieve 99.5% or more.Water is synthesis gas The by-product of conversion process, in the presence of water gas converting catalyst such as methanol synthesis catalyst and cobaltmolybdate catalyst, water and CO Reaction generates CO₂And H₂。

Discovery can break heat present in Production of methanol by the technique of direct preparation of dimethyl ether by using synthesis gas recently Mechanical balance limitation.Document PS Sai Prasad etc., Fuel Processing Technology, volume 89,12 phases, 2008 December, 1281-1286 pages of report, the process are etherified generation by methanol using methanol as intermediate product on acid function catalyst Dimethyl ether.

So another aspect of the present invention is to provide the mixed catalyst of synthesis gas conversion production hydrocarbon compound, this is mixed Close catalyst include: syngas conversion catalyst and dehydration/hydrogenation catalyst, the dehydration/hydrogenation catalyst include molecular sieve or Metal-modified molecular sieve is made from it, wherein the silica alumina ratio of the molecular sieve is 50 or higher, preferably 100 or higher.

Syngas conversion catalyst includes methanol synthesis catalyst and/or dimethyl ether synthetic catalyst.Synthesis gas conversion is urged Agent may include copper oxide, also may include molecular sieve or γ-Al₂O₃。

Syngas conversion catalyst can be for example comprising methanol synthesis catalyst, such as Cu-ZnO- carrier, Pd- carrier, Zn- Cr- carried catalyst.Carrier can be aluminium oxide, silica and/or molecular sieve.Preferably synthetic gas reforming catalyst includes Cu-ZnO-Al₂O₃。

Syngas conversion catalyst can also be for example comprising dimethyl ether synthetic catalyst.Dimethyl ether synthetic catalyst can wrap Carrier containing Cu-ZnO- and Cu-Pd/CeO₂Carrier, wherein carrier can be aluminium oxide, silica and/or molecular sieve.It is preferred that With Al₂O₃For the dimethyl ether synthetic catalyst of carrier.Therefore syngas conversion catalyst may include Cu-ZnO-Al₂O₃/ZSM-5 Or Cu-ZnO-Al₂O₃/γ-Al₂O₃.Therefore syngas conversion catalyst may include composite catalyst.

It also include molecular sieve in first segment catalyst or syngas conversion catalyst in some examples.First segment catalyst The silica alumina ratio of molecular sieve is big in the no second segment catalyst of influence that the silica alumina ratio of middle molecular sieve is distributed product.Some examples In, silica alumina ratio of the silica alumina ratio of molecular sieve lower than molecular sieve in second segment catalyst in first segment catalyst.For example, first segment is urged The silica alumina ratio of molecular sieve is 100 hereinafter, or 70 hereinafter, or 50 or less in agent.

The present invention also provides the catalyst that synthesis gas converts production saturated hydrocarbons, which includes molecular sieve or metal Modified molecular sieve is made from it, wherein the silica alumina ratio (SiO of the molecular sieve₂/Al₂O₃Molar ratio) it is 50 or higher, it is excellent Select 100 or higher.

The present invention also provides the preparation methods of catalyst.

In some examples, the preparation method includes the preparation of mixed catalyst, including such as by syngas conversion catalyst The step of methanol synthesis catalyst is mixed with dehydration/hydrogenation catalyst, such as mechanical mixture.Synthesis gas can be in mixed catalyst On be converted into saturated hydrocarbons, especially C₅And C₅Above saturated hydrocarbons.

The present invention also provides dehydration/hydrogenation catalysts of the invention to be converted into the catalyzed conversion mistake of saturated hydrocarbons in synthesis gas Purposes in journey.Further aspect of the present invention provide by syngas catalytic conversion be saturated hydrocarbons technique, including use dehydration/add Hydrogen catalyst, the dehydration/hydrogenation catalyst include molecular sieve or metal-modified molecular sieve or are made from it, wherein described The silica alumina ratio of molecular sieve is 50 or higher, preferably 100 or higher.Preferably, dehydration/hydrogenation catalyst is placed in comprising methanol And/or in the gaseous mixture of dimethyl ether and hydrogen.The catalyst may include dehydration/hydrogenation catalyst and other catalyst, example Such as syngas conversion catalyst, such as methanol synthesis catalyst.

The technique preferably carries out in the gas phase.Using synthesis gas as raw material, reaction temperature can be about 260-400 DEG C, such as About 250-335 DEG C.Reaction pressure can be about 0.5-6.0MPa, such as from about 2.0-3.0MPa.Reaction velocity can be in about 500- 6000 h^-1Between, such as from about 1000-1500h^-1Between.Preferably, reaction velocity is defined as the unit time and is urged by unit volume The gas flow of agent.

In some examples, first segment catalyst is syngas conversion catalyst, and second segment catalyst is dehydration/hydrogenation catalyst Agent.First segment and second segment can be physically separated from one another, or layering separates filling, or layering filling interlayer has contact surface, or fills out It is intermediate in reactor to be separated with inert media, or load in other ways.Under these filling modes, catalyst be can be not It uniformly loads, some region syngas conversion catalyst concentration are high, some region dehydrations/hydrogenation catalyst concentration is high.Synthesis Gas reforming catalyst is generally in dehydration/hydrogenation catalyst upstream.In some examples, the technique may include turning comprising synthesis gas The upstream catalyst bed changing catalyst or being made from it, such as dimethyl ether synthetic catalyst and/or methanol synthesis catalyst.Therefore The technique can carry out in multistage system.For example, syngas conversion catalyst such as methanol synthesis catalyst and/or dimethyl ether close It can be filled in first segment at catalyst, and dehydration/hydrogenation catalyst is filled in second segment.In some examples, this two sections are point It opens.It, can preferably respective process conditions of independent optimization in two sections of separated situations of reaction system.For certain realities Example, which is that methanol synthesis catalyst and/or dimethyl ether synthetic catalyst can be under optimum process conditions Operation, improves reaction-ure conversion-age, the service life of selectivity of product and catalyst.

In addition, the present invention also provides synthesis gas to convert production C₃And C₃Above saturated hydrocarbons, especially C₅And C₅Above The integrated technique of saturated hydrocarbons, the technique is the following steps are included: it includes catalyst that (a), which feeds the feeding gas comprising synthesis gas, The reaction system of system, the catalyst system include first segment catalyst and second segment catalyst or are made of them；And (b) The product stream in reaction system is removed, which includes C₃And C₃Above saturated hydrocarbons, especially C₅And C₅Above is full And hydrocarbon.First segment catalyst includes dimethyl ether synthetic catalyst and/or methanol synthesis catalyst, second segment catalysis in reaction system Agent includes molecular sieve or metal-modified molecular sieve, and the silica alumina ratio of the molecular sieve is 50 or higher, preferably 100 or higher.

Reaction unit can be one section of reaction system, therefore the technique may include feeding feeding gas by the inclusion of synthesis The step of gas reforming catalyst and dehydration/hydrogenation catalyst or the single catalyst bed system being made of them.

The temperature of catalyst bed is preferably at 300 DEG C or more.

Syngas conversion catalyst can be methanol synthesis catalyst and/or dimethyl ether synthetic catalyst.

It may include metal Pd and/or the source Cu in dehydration/hydrogenation catalyst, also may include ZSM-5 molecular sieve.

Feeding gas can also be fed to dual catalyst bed system, wherein at least part feeding gas is in first segment catalyst It is converted into intermediate product stream on bed, and at least partly intermediate product stream is fed into second segment catalyst bed and further turns Turn to hydro carbons.

First segment reaction temperature is preferably shorter than second segment reaction temperature.Such as first segment reaction temperature reacts temperature than second segment Spend at least low 20 DEG C or 50 DEG C at least low.First segment reaction temperature can be lower than 300 DEG C.First segment reaction temperature is preferably shorter than 295 DEG C, or it is no more than 280 DEG C, or be no more than 250 DEG C.In some examples, first segment reaction temperature is between 190-250 DEG C, example Such as between 210-230 DEG C.It in practical operation, may be changed through entire conversion zone reaction temperature, at this time the conversion zone Reaction temperature is preferably measured as the mean temperature of entire conversion zone.

Second segment reaction temperature can be at 300 DEG C or more.

In some examples, second segment reaction temperature is 320 DEG C or higher.Reaction temperature is preferably 340 in some examples DEG C or it is higher.In some examples, second segment reaction temperature is between about 330-360 DEG C.It is most in order to extend the service life of catalyst In the case of, preferably second segment reaction temperature is lower than 450 DEG C, such as less than 420 DEG C, such as less than 400 DEG C.It is produced depending on target Object can also use other temperature for second segment.

First segment and second segment reaction can carry out at the same pressure, can also carry out at various pressures.Two Duan Fanying can be carried out under the pressure for example no more than 40 bars.In some examples, preferably second segment reaction pressure is than first Section reaction pressure is low, and such as low at least 5 bars, such as low at least 10 bars.

For example, first segment reaction pressure can be lower than 40 bars, or it is lower than 20 bars, or is lower than 10 bars.The reaction of some examples It needs to carry out at a higher pressure.

For example, the reaction pressure of second segment can be lower than 20 bars, or it is lower than 10 bars, or is lower than 5 bars.Some examples are also required to It carries out at a higher pressure.

The gas space velocity of first segment reaction can be for example between about 500 and 6000, such as between about 500-3000.

The gas space velocity of second segment reaction can be for example between about 500-20000, such as between about 1000-10000.

Gas space velocity is defined as, and under standard temperature and pressure (STP), passes through the gas stream of per volume of catalyst in the unit time Amount.

The two-stage reaction can be configured using a variety of reactions to carry out.For example, two sections anti-in the poor example of flexibility It is carried out in separated region in Ying Yi reactor.Within the system, it may be necessary to heat transfer region is provided, such as Independently control the temperature of two conversion zones.

It operates in relatively flexible example, two-stage reaction carries out in separated reactor.Leave first reactor At least part of intermediate product stream (or effluent) is preferably directly entered in second reactor.In some instances, base All intermediate product streams flow into second reactor in sheet.

It is appreciated that can add additional second segment into the intermediate product stream of second segment upstream flows into component.Example Hydrogen and/or DME can such as be added.The intermediate product stream can be subjected to additional operation such as heat exchange in second segment upstream And/or pressure adjustment, such as depressurize.In addition, the outflow component of second segment reaction can reenter the with intermediate product stream In second-stage reaction.

Each conversion zone can use any type of catalyst bed, such as fixed bed, fluidized bed, moving bed.First and The bed type of two conversion zones can be the same or different.

Such as second segment catalyst bed can be moving bed or pairs of bed system (paired bed system), such as Bed system (swing bed system) is waved, this is highly advantageous to catalyst regeneration.

The feeding gas of the technique includes CO/CO₂And H₂.Any type of oxycarbide (such as carbon monoxide and/or dioxy Change carbon) and hydrogen all can serve as feeding gas.There are many production CO/CO at present₂And H₂The technique of gaseous mixture.Every kind of technique is existing Advantage, there is also certain disadvantages.Suitable gas-making process can be selected according to the economy of technique and the availability of raw material, together When can also be according to (H in gaseous mixture product₂-CO₂):(CO+CO₂) the suitable gas-making process of molar ratio selection.Meaning of the invention Synthesis gas is usually CO and/or CO₂With H₂Gaseous mixture.Synthesis gas can be for example from natural gas, petroleum, biomass, carbonaceous material Such as coal, regenerated plastics, municipal refuse, or other organic materials, by the partial oxidation (POX) of hydrocarbon, steam reformation (SR) is first (AGHR) is reformed into gas heating, (such as such as patent US6, described in 284,217) is reformed in microchannel, and plasma is reformed, self-heating Techniques such as (ATR) and their any combination are reformed to prepare.

Discussion in relation to synthesis gas preparation process is in " Hydrocarbon Processing " V78, N.4,87-90, 92-93 (in April, 1999) and " Petrole et Techniques ", N. 415,86-93 have in (the 7-8 month in 1998) Report, the two are both incorporated herein by reference.

Synthesis gas (H used in the present invention₂-CO₂):(CO+CO₂) molar ratio is preferably between 0.6 ~ 2.5.Due to for example Gas recycles in reaction system, by the gas composition of catalyst bed is typically different than the range.For example, in industry To change in Production of methanol, the molar ratio (with above-mentioned definition) of feed synthesis gas is usually 2:1, and after exhaust gas recirculation, It could possibly be higher than 5:1 by the gas mole ratio (with above-mentioned definition) of catalyst bed.In two-stage process, it is catalyzed by first segment The gas initial molar ratio (with above-mentioned definition) of agent bed can be for example between about 0.8-7, such as between about 2-3.

Syngas conversion catalyst, as methanol synthesis catalyst usually has Water gas shift/WGS active.CO and H₂Water occurs for O Gas shift reaction generates H₂And CO₂.The reaction condition of methanol synthesis catalyst (such as first segment catalyst bed) is preferably advantageous In H₂And CO₂Generation.In the example that syngas conversion catalyst is methanol synthesis catalyst, needed for stoichiometric reaction Synthesis gas molar ratio (with above-mentioned definition) is 2:1.It is secondary in the example that syngas conversion catalyst is dimethyl ether synthetic catalyst Product water and CO occur water gas shift reaction and generate H₂And CO₂.In this case, synthesis gas molar ratio (with above-mentioned definition) It is required that being similarly 2:1, but reaction product is CO at this time₂.The second part of reaction can be the methanol synthesized in first segment reaction It is converted into dimethyl ether and water first in second segment reaction, then dimethyl ether conversion is at C₃And C₃More than, especially C₅And C₅With On saturated hydrocarbons and water；It is also possible to the dimethyl ether synthesized in first segment reaction, is directly converted into C in second segment reaction₃ And C₃More than, especially C₅And C₅Above saturated hydrocarbons and water.When using composite catalyst, both conversion zones may exist In in same reactor.

The catalyst that the technique uses can take the circumstances into consideration to include any catalyst as described herein.

On the first catalyst bed, syngas conversion catalyst can be used to prepare methanol and/or dimethyl ether.Synthesis gas Reforming catalyst may include copper oxide and/or molecular sieve and/or γ-Al₂O₃。

Dehydration/hydrogenation catalyst may include the source Pd and/or Cu, also may include ZSM-5 molecular sieve.Second segment bed Reaction temperature can be at 300 DEG C or more.

There is provided the devices for implementing present invention process for another aspect of the present invention.It also provides used in apparatus of the present invention Dehydration/hydrogenation catalyst.The device for processes described herein is additionally provided, and passes through or can pass through methods described herein Dehydration/hydrogenation catalyst of acquisition.

In aspects of the present invention, the preferably described synthesis gas includes the H of 5-83 volume %₂, and H₂/ CO molar ratio is 0.5-5.0, surplus N₂、CO₂, methane, one of inert gas and water vapour or a variety of.

Particularly, the present invention provides the technical solutions of following aspect:

● 1. is a kind of for synthesis gas conversion C processed₅₊Dehydration/hydrogenation catalyst in saturated hydrocarbons multistage catalyst system, It is characterized in that, dehydration/the hydrogenation catalyst is by the solid acid material composition comprising molecular sieve or metal modified molecular screen, Described in molecular sieve or metal modified molecular screen silica alumina ratio 100 or more.

● 2. dehydration/hydrogenation catalysts according to aspect 1, wherein described for being dehydrated/point of hydrogenation catalyst The silica alumina ratio of son sieve is 140 or more.

● 3. dehydration/hydrogenation catalysts according to any one of aspect 1-2, wherein the molecular sieve refers to ZSM-5 molecular sieve.

● 4. dehydration/hydrogenation catalysts according to any one of aspect 1-3, wherein the metal modified molecular screen In metal be one of Pd, Pt, Rh, Ru and Cu or a variety of, wherein it is preferred that Pd and/or Cu.

● 5. is a kind of for synthesis gas conversion C processed₅₊The multistage catalyst system of saturated hydrocarbons, the catalyst system include closing The one section of catalyst formed at gas reforming catalyst and two sections or multistage catalyst being made of dehydration/hydrogenation catalyst, it is special Sign is: dehydration/hydrogenation catalyst of catalyst system is by the solid acid substance comprising molecular sieve or metal modified molecular screen Composition, wherein the silica alumina ratio of molecular sieve or metal modified molecular screen is 100 or more.

● 6. a kind of composite catalysts that hydrocarbon processed is converted for synthesis gas, it is characterised in that the catalyst is turned by synthesis gas Change catalyst and molecular sieve and/or metal modified molecular screen composition, wherein the silica alumina ratio of molecular sieve is 100 or more.

● 7. multistage catalyst system or composite catalysts according to any one of aspect 5-6, wherein the conjunction It include methanol synthesis catalyst at gas reforming catalyst.

● 8. multistage catalyst system or composite catalysts according to any one of aspect 5-7, wherein the conjunction It include dimethyl ether synthetic catalyst at gas reforming catalyst.

● 9. multistage catalyst system or composite catalysts according to any one of aspect 5-8, wherein the conjunction It include copper oxide at gas reforming catalyst.

● the 10. multistage catalyst systems according to aspect 5, wherein the syngas conversion catalyst contains molecule Sieve or γ-Al₂O₃。

● 11. multistage catalyst system or composite catalysts according to any one of aspect 5-9, wherein the gold Belong to modified molecular screen and contains element Pd and/or Cu.

● 12. is a kind of by synthesis gas conversion C processed₅₊The technique of saturated hydrocarbons, it is characterised in that the technique the following steps are included:

(a) synthesis gas is fed into a reaction system containing catalyst system, which is urged by one section Agent and two sections of catalyst compositions；

(b) product hydrocarbon is isolated from reaction system, product hydrocarbon includes C₅₊Saturated hydrocarbons,

Wherein, one section of catalyst of reaction system contains DME synthesis and/or methanol synthesis catalyst；Two sections of catalyst Containing molecular sieve or metal modified molecular screen, the silica alumina ratio of molecular sieve is 100 or more.

● 13. techniques according to aspect 12, wherein by synthesis gas feed one containing one section of catalytic component and The complex catalyst system of two sections of catalytic components.

● 14. techniques according to aspect 13, wherein the bed temperature of complex catalyst system is at 300 DEG C when reaction More than.

● 15. techniques according to any one of aspect 12-14, wherein one section of catalytic component is production first Alcohol active component.

● 16. techniques according to any one of aspect 12-15, wherein one section of catalytic component is production two Methyl ether active component.

● 17. techniques according to aspect 12, wherein synthesis gas is fed into the reaction system containing two-stage catalytic agent, Wherein two-stage catalytic agent does not contact, to guarantee that at least Partial Conversion generates intermediate products to synthesis gas on one section of catalyst, together When the intermediate products that at least partially generate be injected on two sections of catalyst and reacted.

● 18. techniques according to aspect 17, wherein one section of catalyst being capable of catalysis methanol synthesis.

● 19. techniques according to any one of aspect 17-18, wherein one section of catalyst can be catalyzed diformazan Ether synthesis.

● 20. techniques according to any one of aspect 17-19, wherein two sections of catalyst bed reaction temperature At 300 DEG C or more.

● 21. techniques according to any one of aspect 12-20, wherein metal-modified point of two sections of catalyst The metal of son sieve includes Pd and/or Cu.

● 22. techniques according to any one of aspect 12-20, wherein the molecular sieve of two sections of catalyst refers to ZSM-5 molecular sieve.

● it is 23. dehydration/hydrogenation catalysts according to any one of aspect 1-22, multistage catalyst system, compound Catalyst or technique, wherein the H of the synthesis gas₂Volumetric concentration is 5-83%, H₂/ CO molar ratio is 0.5-5.0, surplus N₂、 CO₂, methane, inert gas, one of water vapour or two kinds or more.

Other aspects that any feature of the present invention in a certain respect can be used for inventing, can also optionally carry out appropriate group It closes.As it can be applied to device in terms of method characteristic in terms of, vice versa.

Below by way of specific example and attached drawing, it is illustratively described the main feature of the present invention.

Detailed description of the invention

Attached drawing instantiates technique according to the present invention and/or device.

Fig. 1 schematically shows that two sections of the synthesis gas conversion production saturated hydrocarbons that an embodiment of the present invention uses are anti- Answer device system.

Specific embodiment

Two reactor system 1 shown in FIG. 1 is shown by the process of synthesis gas saturated hydrocarbons.System 1 includes two strings Join the conversion zone 3 and 5 of connection.Each conversion zone include comprising fixed bed catalyst system reactor and equipped with temperature controller Stove, the internal diameter of tubular reactor are 12mm.Reaction carries out under an increased pressure, and 21,21 ' be counterbalance valve, under reactor Trip.When implementing includes the embodiment of a catalyst section, using only the reactor of first segment 3.

First segment catalyst in the conversion zone 3 of upstream is mainly methanol synthesis catalyst；The conversion zone 5 in downstream is equipped with the Two sections of catalyst, including dehydration/hydrogenation catalyst.

Synthesis gas passes sequentially through pressure gauge P1, pressure reducing valve 9, pressure gauge P2, the flow equipped with shut-off valve through feeding line 7 11, pressure gauge P3 are counted, into the first conversion zone 3.Nitrogen feed pipeline 13 is set as N₂It is fed at pressure gauge P1.Hydrogen into Expects pipe line 15 and exhaust line 17 are arranged in 9 upstream of pressure reducing valve.Intermediate product stream is from the first conversion zone 3 by pipeline 19 through carrying on the back Pressure valve leads to pressure gauge P4, then enters the second conversion zone 5.Product stream is flowed out from the second conversion zone 5 through pipeline 23 to downstream Counterbalance valve 21 ', enter back into the analysis system in downstream.

The downstream of reaction system is equipped with gas-chromatography 25, and chromatographic analysis system receives the intermediate product stream from pipeline 19 And/or the product stream from pipeline 23.Gas-chromatography 25 is equipped with flame ionization detector (FID) and thermal conductivity detector (TCD) (TCD)。

Catalyst estimation

In embodiment, catalyst activates two hours first in flow of pure hydrogen at 250 DEG C.Then hydrogen is switched to Synthesis gas is reacted under the conditions of differential responses as described below.All products come out out of reactor are gas phase, and Pass through gas-chromatography on-line analysis.CO,CO₂、CH₄And N₂Gas chromatographic analysis of the component equipped with TCD detector, organic matter are used Another gas chromatographic analysis equipped with fid detector.

Embodiment 1:

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst (Shenyang Catalyst Plant) is crushed to 20-40 mesh 20-40 mesh particle is pelletized and are crushed to grain, ZSM-5 molecular sieve (Nankai University's catalyst Co.).Weigh 0.35g Cu-Zn- Al methanol synthesis catalyst particle and 0.45g ZSM-5 (SiO₂/Al₂O₃=140) sieve particle uniformly mixes.In reaction temperature 300 DEG C, pressure 2.0MPa, synthesis gas (H of degree₂/ CO=1/1) flow 25ml/min operating condition under assess catalyst performance.

CO conversion ratio is 58.7%, CO in product₂Selectivity is 52.5%, and the overall selectivity of methanol and dimethyl ether is 0.1%, The selectivity of hydro carbons is 47.4%.The distribution of hydro carbons is as shown in table 1 in product.Gasoline (C in hydro carbons_5-11) selectivity 30% with Under, light gasoline fraction C_5-8The selectivity of middle isoparaffin is very high, and the selectivity of aromatic hydrocarbons and alkene is very low.C_9-11Virtue in fraction Hydrocarbon is mainly trimethylbenzene and durol.

Hydrocarbon distribution in 1 embodiment 1 of table

Data in table are the selectivity of product % of the technique, are measured as %C.

Embodiment 2

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst (Shenyang Catalyst Plant) is crushed to 20-40 mesh 20-40 mesh particle is pelletized and are crushed to grain, ZSM-5 molecular sieve (Nankai University's catalyst Co.).Weigh 0.35g Cu-Zn- Al methanol synthesis catalyst and 0.45g ZSM-5 (SiO₂/Al₂O₃=140) series connection is filled into reactor up and down for molecule screening, and two Catalyst bed interlayer is contacted with each other by interface.At 290 DEG C of reaction temperature, pressure 2.0MPa, synthesis gas (H₂/ CO=1/1) flow Catalyst performance is assessed under the operating condition of 25ml/min.

CO conversion ratio is 32.9%, CO in product₂Selectivity is 51.5%, and the overall selectivity of methanol and dimethyl ether is 0.2%, The selectivity of hydro carbons is 48.3%.It is not limited to specific theory, it is believed that series connection loads two kinds of catalyst and reduces the association between catalyst Same-action, so that the conversion ratio of CO is than low in embodiment 1.But C in product_5-11Selectivity increased, in product Hydrocarbon distribution is as shown in table 2.

Hydrocarbon distribution in 2 embodiment 2 of table

Embodiment 3

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst and γ-Al₂O₃It is uniform with 9/5 powder of mass ratio Mixing, then pelletize and be crushed to the catalyst granules of 20-40 mesh.The catalyst is labeled as composite catalyst I.Using ion exchange Method prepares the modified ZSM-5 molecular sieve of Metal Palladium.The preparation method is as follows:

10g ZSM-5 molecular sieve is slowly added to 200ml PdCl₂In solution, stirred at a temperature of 60 DEG C, ion exchange 8h, then be washed with deionized water, it filters, it is dry at a temperature of 120 DEG C, then in 550 DEG C of roasting temperatures, then pelletizes and crush At the catalyst granules of 20-40 mesh.Catalyst is labeled as 0.5%Pd-ZSM-5.

Weigh 0.6g composite catalyst I particle and 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃=140) particle uniformly mixes It closes.At 300 DEG C of reaction temperature, pressure 2.0MPa, synthesis gas (H₂/ CO=1/1) flow 25ml/min operating condition under assess and urge Agent performance.CO conversion ratio is 72.3%, CO in product₂Selectivity is 52.8%, and the overall selectivity of methanol and dimethyl ether is 0.2%, The selectivity of hydro carbons is 47.0%.The distribution of hydrocarbon is as shown in table 3 in product.

Hydrocarbon distribution in 3 embodiment 3 of table

Embodiment 4

Weigh 0.6g composite catalyst I and 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃=140) series connection loads, two catalysis It is contacted with each other between agent bed by interface.At 300 DEG C of reaction temperature, pressure 3.0MPa, synthesis gas (H₂/ CO=1/1) flow Catalyst performance is assessed under the operating condition of 35ml/min.

CO conversion ratio is 62.3%, CO in product₂Selectivity is 50.1%, and the selectivity of hydrocarbon is 49.9%.Hydrocarbon point in product Cloth is as shown in table 4.γ-Al in composite catalyst I₂O₃Dimethyl ether is converted by the methanol of generation, so CO conversion ratio compares embodiment Height in 2, but the hydrocarbon distribution in product is compared with Example 2, does not change much.

Hydrocarbon distribution in 4 embodiment 4 of table

Embodiment 5

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment catalyst bed It is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.It is 3.0MPa, synthesis gas (H in reaction pressure₂/CO=1/ 1) catalyst performance is assessed under the operating condition that flow is 25ml/min.CO conversion ratio is 62.5%, CO₂Selectivity is 34.6%, The overall selectivity of methanol and dimethyl ether is 0.3% in product, and the selectivity of hydrocarbon is 65.1%.Hydrocarbon distribution in product is as shown in table 5.

Hydrocarbon distribution in 5 embodiment 5 of table

Embodiment 6

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment catalyst bed It is 294 DEG C, the reaction temperature of second segment catalyst bed is 330 DEG C.It is 4.0MPa, synthesis gas (H in reaction pressure₂/CO=1/ 1) catalyst performance is assessed under the operating condition that flow is 25ml/min.CO conversion ratio is 67.4%, CO₂Selectivity is 34.4%, The overall selectivity of methanol and dimethyl ether is 1.7% in product, and the selectivity of hydrocarbon is 63.9%.Hydrocarbon distribution in product is as shown in table 6.

Hydrocarbon distribution in 6 embodiment 6 of table

Embodiment 7

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst and ZSM-5 (SiO₂/Al₂O₃=50) molecular sieve with The mixing of 9/5 powder of mass ratio, pelletizes and is crushed to 20-40 mesh particle.Labeled as composite catalyst II.

Weighing 0.6g composite catalyst II is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two-stage catalytic agent bed is separated without directly contact.The reaction temperature of first segment catalyst bed Degree is 265 DEG C, and the reaction temperature of second segment catalyst bed is 301 DEG C.It is 2.0MPa, synthesis gas (H in reaction pressure₂/CO= 1/1) catalyst performance is assessed under the operating condition that flow is 25ml/min.

CO conversion ratio is 47.3%, CO₂Selectivity is 38.1%, and the overall selectivity of methanol and dimethyl ether is 0.1% in product, The selectivity of hydrocarbon is 61.8%.Hydrocarbon distribution in product is as shown in table 7.When two kinds of catalyst are separated in two catalyst beds C when in layer, in hydrocarbon products₅-C₁₁The selectivity of component is higher.

Hydrocarbon distribution in 7 embodiment 7 of table

Embodiment 8

Weighing 0.6g composite catalyst II is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two-stage catalytic agent bed is separated without directly contact.The reaction temperature of first segment catalyst bed Degree is 282 DEG C, and the reaction temperature of second segment catalyst bed is 321 DEG C.It is 3.0MPa, synthesis gas (H in reaction pressure₂/CO= 1/1) catalyst performance is assessed under the operating condition that flow is 25ml/min.

CO conversion ratio is 66.6%, CO₂Selectivity is 43.1%, and the selectivity of hydrocarbon is 56.9%, does not have methanol and two in product Methyl ether.Hydrocarbon distribution in product is as shown in table 8.

Hydrocarbon distribution in 8 embodiment 8 of table

Embodiment 9

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst and ZSM-5 (SiO₂/Al₂O₃=140) molecular sieve With the mixing of 9/5 powder of mass ratio, pelletizes and be crushed to 20-40 mesh particle.Labeled as composite catalyst III.

Weighing 0.6g composite catalyst III is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two-stage catalytic agent bed is separated without directly contact.The reaction temperature of first segment catalyst bed Degree is 282 DEG C, and the reaction temperature of second segment catalyst bed is 321 DEG C.It is 3.0MPa, synthesis gas (H in reaction pressure₂/CO= 1/1) catalyst performance is assessed under the operating condition that flow is 25ml/min.CO conversion ratio is 50.2%, CO₂Selectively it is 35.9%, the selectivity of hydrocarbon is 64.1%, does not have methanol and dimethyl ether in product.Hydrocarbon distribution in product is as shown in table 9.

Hydrocarbon distribution in 9 embodiment 9 of table

Embodiment 10

Commercially available Cu-ZnO-Al₂O₃(Cu-Zn-Al) methanol synthesis catalyst, γ-Al₂O₃With ZSM-5 (SiO₂/Al₂O₃= 140) molecular sieve is pelletized with the mixing of mass ratio 9:5:10 powder and is crushed to 20-40 mesh particle.The catalyst is urged labeled as compound Agent IV.

Weigh 1.65g composite catalyst IV and 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃=140) layer series load, Two catalyst bed interlayers are contacted with each other by interface.At 300 DEG C of temperature, reaction pressure 2.0MPa, synthesis gas (H₂/CO=1/1) Catalyst performance is assessed under the operating condition that flow is 50ml/min.

CO conversion ratio is 47.9%, CO₂Selectivity is 51.8%, and the selectivity of hydrocarbon is 47.4%, total choosing of methanol and dimethyl ether Selecting property 0.8%.Hydrocarbon distribution in product is as shown in table 10.

Hydrocarbon distribution in 10 embodiment 10 of table

Embodiment 11

Weigh 0.6g composite catalyst I and 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃=140) catalyst granules mixes Uniformly, the catalyst and 0.45g 0.5%Pd-ZSM-5 (SiO which mixed₂/Al₂O₃=140) catalyst layer series are filled out It fills, is contacted with each other between two-stage catalytic agent bed by interface.At 290 DEG C of temperature, reaction pressure 2.0MPa, synthesis gas (H₂/CO =1/1) catalyst performance is assessed under the operating condition that flow is 50ml/min.

CO conversion ratio is 57.5%, CO₂Selectivity is 48.2%, and the selectivity of hydrocarbon is 51.4%, total choosing of methanol and dimethyl ether Selecting property 0.4%.Hydrocarbon distribution in product is as shown in table 11.

Hydrocarbon distribution in 11 embodiment 11 of table

Embodiment 12

The modified ZSM-5 molecular sieve catalyst of Cu is prepared with equi-volume impregnating.Method is as follows: with Cu (NO₃)₂ ^.3H₂O is Presoma, dissolution is in deionized water.About 10ml solution is added dropwise in about 10g ZSM-5 molecular sieve in 5 minutes, at room temperature Dipping is for 24 hours, then dry at 90 DEG C, roasts 4h at 400 DEG C.Prepared catalyst is labeled as xCu-ZSM-5, and wherein x refers to The mass fraction of copper.

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 5%Cu-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment catalyst bed It is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.It is 3.0MPa, synthesis gas (H in reaction pressure₂/CO=1/ 1) catalyst performance is assessed under the operating condition that flow is 25ml/min.CO conversion ratio is 60.9%, CO₂Selectivity is 35.7%, The overall selectivity of methanol and dimethyl ether is 3.4% in product, and the selectivity of hydrocarbon is 60.9%.Hydrocarbon in product is distributed such as 12 institute of table Show.

Hydrocarbon distribution in 12 embodiment 12 of table

Embodiment 13

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 10%Cu-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment catalyst bed It is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.It is 3.0MPa, synthesis gas (H in reaction pressure₂/CO=1/ 1) catalyst performance is assessed under the operating condition that flow is 25ml/min.CO conversion ratio is 62.4%, CO₂Selectivity is 36.2%, The overall selectivity of methanol and dimethyl ether is 3.3% in product, and the selectivity of hydrocarbon is 60.5%.Hydrocarbon in product is distributed such as 13 institute of table Show.

Hydrocarbon distribution in 13 embodiment 13 of table

Embodiment 14

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 360) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment catalyst bed It is 294 DEG C, the reaction temperature of second segment catalyst bed is 330 DEG C.It is 4.0MPa, synthesis gas (H in reaction pressure₂/CO=4/ 1) catalyst performance is assessed under the operating condition that flow is 50ml/min.

CO conversion ratio is 78.8%, due to inhibiting water gas shift reaction, CO under rich hydrogen condition₂Selectivity is reduced to 23.7%, there is no methanol and dimethyl ether in product, the selectivity of hydrocarbon is 76.3%.Hydrocarbon distribution in product is as shown in table 14.

Hydrocarbon distribution in 14 embodiment 14 of table

Embodiment 15

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment reaction bed is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.The pressure of reaction is 3.0MPa, synthesis gas (H₂/CO=1/1) Flow be 25ml/min.Investigate stability (short-term life test (the short term life reacted under the reaction conditions test))。

When runing time is 1h, CO conversion ratio is 61.8%, CO₂Selectivity is 34.5%, and the selectivity of hydrocarbon is 65.4%, first The overall selectivity of pure and mild dimethyl ether is 0.1%.Hydrocarbon in product is distributed as shown in table 15-1.

When runing time is 9h, CO conversion ratio is 61.3%, CO₂Selectivity is 35.0%, and the selectivity of hydrocarbon is 62.3%, first The overall selectivity of pure and mild dimethyl ether is 2.7%.Hydrocarbon in product is distributed as shown in table 15-2.

When runing time is for 24 hours, CO conversion ratio is 58.9%, CO₂Selectivity is 34.4%, and the selectivity of hydrocarbon is 58.2%, first The overall selectivity of pure and mild dimethyl ether is 7.4%.Hydrocarbon in product is distributed as shown in table 15-3.

The selectivity of methanol and dimethyl ether increases with the running time increases.This may be as the reaction time prolongs Long, the water separation capability of catalyst reduces.Olefin component in product increases, this may be since the hydrogenation capability of catalyst declines Caused.

After 24 hours stability tests, increases reaction pressure to 4.0MPa, increase the reaction temperature of second segment catalyst bed It spends to 330 DEG C.When runing time is 31h, CO conversion ratio increases to 67.4%, CO₂Selectivity is 34.4%, and the selectivity of hydrocarbon is 63.8%, the C in hydrocarbon_5-11Group is divided into 69.7%, and the overall selectivity of methanol and dimethyl ether is 1.8%.Hydrocarbon distribution such as table in product Shown in 15-4.

Hydrocarbon distribution in 15 embodiment 15 of table

Comparative example 16

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 50) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment reaction bed is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.The pressure of reaction is 3.0MPa, synthesis gas (H₂/CO=1/1) Flow be 25ml/min.It reacts under this condition, the conversion ratio of CO is 61.5%, CO₂Selectivity is 35.6%, the selectivity of hydrocarbon It is 62.8%, the overall selectivity of methanol and dimethyl ether is 1.6%.Hydrocarbon distribution in product is as shown in table 16.

Hydrocarbon distribution in 16 embodiment 16 of table

Embodiment 17

Weighing 0.6g composite catalyst I is first segment catalyst bed, 0.45g 0.5%Pd-ZSM-5 (SiO₂/Al₂O₃= It 140) is second segment catalyst bed.Two catalyst beds are separated without directly contact.The reaction temperature of first segment reaction bed is 282 DEG C, the reaction temperature of second segment catalyst bed is 320 DEG C.The pressure of reaction is 3.0MPa, synthesis gas (H₂/CO=1/1) Flow be 25ml/min.Under the reaction conditions, the conversion ratio of CO is 61.3%, CO₂Selectivity be 34.6%, the selection of hydrocarbon Property be 63.4%, the overall selectivity of methanol and dimethyl ether is 2.0%.Hydrocarbon distribution in product is as shown in table 17.

Hydrocarbon distribution in 17 embodiment 17 of table

Comparative example 18

Catalyst bed loads 0.5g H-ZSM-5 molecular sieve catalyst, at 400 DEG C of reaction temperature, normal pressure, and nitrogen conduct Carrier gas, flow are reacted under conditions of being 25ml/min.The conversion ratio of methanol is 100%, C in product_2-4The selectivity of alkene In C_2-4It is 66% or so, C in hydrocarbon_5-8Aromatic hydrocarbons is main product in fraction, and the selectivity of olefin addition is also very high.It can from table 18 To find out, using methanol as raw material, nitrogen is carrier gas, product generated with it is above-mentioned generated using synthesis gas as the technique of raw material Very big difference is distributed in hydrocarbon in product.

Hydrocarbon distribution in 18 comparative example 18 of table

It should be appreciated that illustrative explanation only has been made to the present invention above, it within the scope of the present invention can be to above disclosure Details make various changes.Each feature disclosed in specification and (if applicable) claims and drawing can be with It individually uses or uses in any suitable combination.

Claims

1. dehydration/hydrogenation catalyst can be used in the multistage catalyst system for synthesis gas conversion production C5+ saturated hydrocarbons In, which is characterized in that the catalyst system includes at least one section of catalyst and two sections of catalyst, wherein one section of catalyst includes to close At gas reforming catalyst or it is made from it, two sections of catalyst include dehydration/hydrogenation catalyst or are made from it, the dehydration/ Hydrogenation catalyst includes solid acid substance or is made from it, which includes molecular sieve and/or metal-modified point Son sieve, wherein the silica alumina ratio of the molecular sieve and/or metal modified molecular screen is 120 or more.

2. dehydration/the hydrogenation catalyst according to claim 1, wherein the molecular sieve and/or metal modified molecular screen Silica alumina ratio 140 or more.

3. according to claim 1 or dehydration/hydrogenation catalyst described in 2, wherein the molecular sieve includes ZSM-5 molecular sieve And/or the metal modified molecular screen includes metal-modified ZSM-5 molecular sieve.

4. dehydration/hydrogenation catalyst according to claim 3, wherein the metal in the metal modified molecular screen is One of Pd, Pt, Rh, Ru and Cu or a variety of.

5. dehydration/hydrogenation catalyst according to claim 4, which is characterized in that wherein in the metal modified molecular screen Metal be Pd and/or Cu.

6. the composite catalyst for synthesis gas conversion production C5+ saturated hydrocarbons, which is characterized in that the composite catalyst includes to close It is formed at gas reforming catalyst and dehydration/hydrogenation catalyst or by them, wherein the dehydration/hydrogenation catalyst includes solid Acidic materials are made from it, which includes molecular sieve and/or metal modified molecular screen or be made from it, Described in molecular sieve and/or metal modified molecular screen silica alumina ratio 120 or more.

7. composite catalyst according to claim 6, wherein the syngas conversion catalyst is urged comprising methanol-fueled CLC Agent.

8. the composite catalyst according to any one of claim 6-7, wherein the syngas conversion catalyst includes two Methyl ether synthetic catalyst.

9. composite catalyst according to claim 8, wherein the syngas conversion catalyst includes copper oxide.

10. composite catalyst according to claim 9, wherein the syngas conversion catalyst include molecular sieve and/ Or γ-Al₂O₃。

11. composite catalyst according to claim 10, wherein the metal modified molecular screen includes Pd and/or Cu.

12. synthesis gas conversion production C5+ saturated hydrocarbons technique, which is characterized in that the technique the following steps are included:

(a) synthesis gas is fed into the reaction system comprising catalyst system, which includes one section of catalyst and two sections Catalyst is made of them；And

(b) product hydrocarbon is isolated from reaction system, which includes C5+ saturated hydrocarbons, wherein one section of catalyst packet Containing DME synthesis and/or methanol synthesis catalyst；Two sections of catalyst include molecular sieve and/or metal modified molecular screen, Described in molecular sieve and/or metal modified molecular screen silica alumina ratio 120 or more.

13. technique according to claim 12, wherein step (a) includes feeding synthesis gas comprising one section of catalyst group Divide the complex catalyst system with two sections of catalytic components.

14. technique according to claim 13, wherein the bed temperature of the complex catalyst system is at 300 DEG C when reaction More than.

15. technique described in any one of 2-14 according to claim 1, wherein one section of catalyst is living with methanol-fueled CLC Property.

16. technique according to claim 15, wherein one section of catalyst has DME synthesis activity.

17. technique according to claim 12, wherein the step (a) includes feeding synthesis gas comprising a Duan Cuihua The reaction system of agent and two sections of catalyst, wherein one section of catalyst is not directly contacted with two sections of catalyst, wherein closing Intermediate product is at least partly converted on one section of catalyst at gas, while at least part of intermediate product generated supplies Enter to being reacted on two sections of catalyst.

18. technique described in 7 according to claim 1, wherein one section of catalyst has methanol-fueled CLC activity.

19. technique described in any one of 7-18 according to claim 1, wherein one section of catalyst has DME synthesis Activity.

20. technique according to claim 19, wherein the bed temperature of two sections of catalyst described in when reaction 300 DEG C with On.

21. technique according to claim 20, wherein the metal modified molecular screen of two sections of catalyst include Pd and/ Or Cu.

22. technique according to claim 21, wherein the molecular sieve of two sections of catalyst include ZSM-5 molecular sieve and/ Or metal modified molecular screen includes metal-modified ZSM-5 molecular sieve.

23. technique according to claim 12, it is characterised in that:

Wherein the synthesis gas includes the H of 5-83 volume %₂, and H₂/ CO molar ratio is 0.5-5.0, surplus N₂、 CO₂, methane, One of inert gas and water vapour are a variety of.