CN108264921A - The method that a kind of Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon - Google Patents
The method that a kind of Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon Download PDFInfo
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- CN108264921A CN108264921A CN201810023906.3A CN201810023906A CN108264921A CN 108264921 A CN108264921 A CN 108264921A CN 201810023906 A CN201810023906 A CN 201810023906A CN 108264921 A CN108264921 A CN 108264921A
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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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- 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
- C10G2/334—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 molecular sieve catalysts
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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
- C10G2/34—Apparatus, reactors
- C10G2/341—Apparatus, reactors with stationary catalyst bed
Abstract
The present invention provides a kind of method that Fischer-Tropsch oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon.It includes the following steps：Unstripped gas is passed through to progress Fischer-Tropsch oligomerisation coupling catalytic reactions in the fixed bed reactors for be mounted with composite catalyst, generates the liquid mixture comprising liquid hydrocarbon and water, stratification obtains upper strata grease i.e. liquid hydrocarbon；The composite catalyst is fischer-tropsch catalysts and the coupled catalyst of catalyst for oligomerization.The present invention can be achieved CO and alkene cotransformation and be distributed Relatively centralized, isomeric olefine advanced liquid hydrocarbon as main component for carbon, have the features such as conversion condition is mild, technique concentration is easy, and carbon utilisation rate is high, and selectivity of product is strong and added value is high.
Description
Technical field：
The invention belongs to rich olefins syngas catalytic conversions to prepare hydro carbons technical field, and in particular to a kind of Fischer-Tropsch-oligomerisation
The method that coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon.
Background technology：
The production of world wide fuel is mainly derived from the refining process of oil.As global oil price is gradually climbed
Rise, a large amount of consumption of petroleum resources and environmental issue (greenhouse effects and discharge pollutants, such as floating carbon, hydrocarbon, an oxidation
Carbon, oxynitrides, sulfide etc.) pay attention to day by day, the regenerative resource technique for developing non-petrochemical industry receives significant attention.Mesh
Before, biomass resource due to it is clean, rich reserves and it is renewable the features such as, be that can uniquely be converted into liquid fuel and height
The carbonaceous resource of added value chemicals, it is considered to be substitute one of optimal selection of fossil resource.
Method using biomass as raw material liquid fuel was prepared (BTL) mainly has biomass F- T synthesis technology, grease to add
Hydrogen treatment technology, biomass pyrolytic and biotransformation method.Wherein, biomass-based F- T synthesis is most suitable commercialized renewable
Using energy source approach.The key in the path is synthesis gas (H2, CO) preparation and conversion, including gasification of biomass, net
Change the processes such as compression, F- T synthesis and cracking.But due to containing sodium, potassium and otheralkali metal element, gasification in biomass
In easily generate that slag is pure and dirt, contaminated equipment.Being introduced into for gasification oxygen also increases N in product2、CO2Etc. foreign gases
Content, while reduce the hydrogen-carbon ratio of synthesis gas, be unfavorable for the transformation efficiency and Fischer-Tropsch synthesis of synthesis gas.
Bio oil is to be mixed by lignocellulose type biomass by the organic liquid that fast pyrolysis liquefaction process generates
Object.Compared with biomass, there is easily collecting, easily storage and the easily advantage of transport etc., had using bio oil inhibition and generation chemical product
The problems such as conducive to the biomass encountered during practical biomass economy dispersibility, inconvenient storage and long-distance transport is solved.In recent years
Come, the catalytic pyrolysis of bio oil is not since it needs to consumption hydrogen, and cheap, reaction does not need to high pressure, and can use for reference oil
The features such as mature experience of catalytic pyrolysis, obtains universal concern.In general, bio oil can pass through Ni/La/ under normal pressure
The catalytic pyrolysis such as HZSM-5 molecular sieve catalysts generate the C of 15%~30% (volume fraction)2-4Low-carbon alkene and 30%~40%
The synthesis gas of (volume fraction).Wherein alkene can be by ALKENE OLIGOMERIZATION TO LIQUID FUELS, and product distribution is not distributed by ASF to be limited
System；And CO therein, H2Active principle can then be converted into the hydro carbons of wide carbon number distribution by F- T synthesis.But the production of F- T synthesis
Object is limited by ASF distributions and mainly based on straight-chain hydrocarbons, is unfavorable for improving the octane number of fuel.Generally speaking, bio oil is catalyzed
Active principle there are two types of containing in cracked gas product, one kind is low-carbon alkene, and another kind of is hydrogen and carbon monoxide.
Invention content：
The object of the present invention is to provide a kind of Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas to prepare liquid hydrocarbon
Method, the achievable CO of the present invention and alkene cotransformation are distributed Relatively centralized, isomeric olefine advanced liquid as main component for carbon
Body hydro carbons has the features such as conversion condition is mild, technique concentration is easy, and carbon utilisation rate is high, and selectivity of product is strong and added value is high.
The object of the present invention is to provide a kind of Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas to prepare liquid hydrocarbon
Method, include the following steps：
It is anti-that unstripped gas is passed through to progress Fischer-Tropsch-oligomerisation coupling and catalyzing in the fixed bed reactors for be mounted with composite catalyst
Should, the liquid mixture comprising liquid hydrocarbon and water is generated, stratification obtains upper oil phase i.e. liquid hydrocarbon；
The composite catalyst is fischer-tropsch catalysts and the coupled catalyst of catalyst for oligomerization.
The above-mentioned method for preparing liquid hydrocarbon, is as follows：
(1) composite catalyst is loaded in fixed bed reactors, replaces synthesis gas at room temperature until fixed bed reactors
After interior air is synthesized gas displacement completely, normal pressure is passed through synthesis gas, while fixed bed reactors are warming up to 300 DEG C~400 DEG C, and
Constant temperature 12h is until fischer-tropsch catalysts fully restore；
(2) fixed bed reactors temperature is reduced to 150 DEG C, is passed through unstripped gas and enters fixed bed reactors, control gas
Air speed is 1500~3000mL/gh, and adjusts fixed bed reactors pressure to 3.0~4.0MPa, improves fixed bed reactors
Temperature makes unstripped gas react in composite catalyst bed to 280 DEG C~320 DEG C；
(3) after step (2) reaction, from the condenser discharge product liquid in fixed bed reactors and incoagulable gas production
Object, incoagulable gas product are the residual raw materials gas for not participating in reaction, and product liquid is layered after standing and obtains oil phase and water phase, oil
It is mutually liquid hydrocarbon.The long chain hydrocarbons that the present invention generates can finally obtain gasoline, lubricating oil etc., the tail of system through down stream processing steps
Gas unreacted unstripped gas after further separation is recycled into fixed bed reactors.
The present invention prepares liquid hydrocarbon and is related to two processes by Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas,
In catalyst for oligomerization bed acidic site active site polymerization, isomerization reaction generation long chain hydrocarbons occur for the low-carbon alkene in unstripped gas
Class, and along with the generation of cracking reaction；At the same time, unreacted H2, CO occurs on fischer-tropsch catalysts metal active position
Carbon-carbon bond coupled reaction generates long-chain hydro carbons；It is final to obtain carbon distribution mainly in C6-C12Isomery hydro carbons.Since alkene is easily taking
Fischer-tropsch catalyst active sites occur plus hydrogen side reaction, and the different coupled mode of use can reach different reaction effects, wherein adopting
The generation for adding hydrogen side reaction is preferably inhibited when being coupled with oligomerisation/Fischer-Tropsch-dual bed, is optimal liquid hydrocarbon yield, product
Optimal olefin ratios are more than 90%, and isomerisation degree is more than 60%, by further hydrogen upgrading being added to can obtain isomerized alkyl
Based on fuel.
The unstripped gas is rich olefins synthesis gas, and the rich olefins synthesis gas includes C2-4Alkene and H2The mixing of/CO
Gas.Rich olefins synthesis gas refers to that active ingredient is C2-C4Alkene and H2, CO gaseous mixture.Petrochemical industry cracking process or life can be derived from
The catalytic pyrolysis of substance, bio oil, the typical C containing 15%~30% (volume fraction) generated such as bio oil catalytic pyrolysis2-
C4Synthesis gas (the H of low-carbon alkene and 30%~40% (volume fraction)2、CO)。
It is preferred that the coupled mode of the composite catalyst is ball milling mixing, mortar grinder mixing, particle mixes or double bed
Layer filling, the active metal component of the fischer-tropsch catalysts is Fe or Co, and catalyst for oligomerization is Si-Al molecular sieve, solid phosphoric acid
Or nickel metal oxide catalyst.
Fischer-tropsch catalysts can be used product distribution and concentrate on all kinds of Co bases of long chain hydrocarbons or Fe base catalyst, can press
The patented methods such as CN1398669B, CN1303738B, CN1454714B, CN1562471B, CN1562476B or CN1597105B
It prepares.Acidic catalyst, such as Si-Al molecular sieve, solid phosphoric acid, nickel metal oxide catalyst can be used in catalyst for oligomerization.Into
One step is preferred, and fischer-tropsch catalysts use FeMn catalyst prepared by coprecipitation, wherein m (Fe):M (Mn)=2:1, oligomerization catalysis
Agent uses commercially available HZSM-5 catalyst, wherein m (Si):M (Al)=20:1.
It is preferred that the FeMn catalyst is prepared by coprecipitation, specific preparation process is as follows：By Fe (NO3)3·
9H2O and Mn (NO3)2It is dissolved in deionized water, stirring to formation uniform solution, the mass ratio of wherein Fe and Mn are 2:1；By institute
The solution stated is heated to 80 DEG C of constant temperature, then under conditions of stirring, instills ammonia spirit dropwise into solution, adjusts solution
PH is 8.0, treats to generate crineous precipitation in solution, and crineous precipitation is completely rear to stand 12h, and obtained crineous is precipitated and is carried out
Post processing obtains the FeMn catalyst of 40~60 mesh (i.e. grain size is 0.25~0.38mm).
It is preferred that the reaction condition described in step (2) is：280 DEG C, reaction pressure 3.0MPa, air speed 1500mL/g of temperature
h。
Unless otherwise indicated, nominal definition of the present invention has is generally understood identical contain with those skilled in the art
Justice.
Compared with prior art, the present invention has the following advantages：The present invention can be filled using Fischer-Tropsch-oligomerisation coupling technique
Divide using alkene and the effective carbon source of carbon monoxide in rich olefins gaseous mixture, improve comprehensive carbon utilisation rate, broken tradition and passed through expense
The shortcomings that hydrocarbon product carbon distribution that support synthesis is prepared using synthetic gas method is limited by ASF distributions, which can obtain
More targetedly concentrate carbon distribution.The use of coupling technique of the present invention can greatly improve the isomerization journey of product hydrocarbonaceous
Degree is conducive to improve the octane number that down stream processing steps obtain fuel, meanwhile, which has simple, process
The advantages of concentration.The abundant biomass resource of available resources of the present invention is raw material, is conducive to green low-carbon and resource is fully sharp
With.
Specific embodiment：
Following embodiment is the further explanation to the present invention rather than limitation of the present invention.
The method that following embodiment Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon is specific
Step is as follows：
(1) composite catalyst is loaded in fixed bed reactors, replaces synthesis gas at room temperature until fixed bed reactors
After interior air is synthesized gas displacement completely, normal pressure is passed through synthesis gas, synthesizes atmospheric pressure 0.1MPa, synthesis gas air speed 3000mL/g
H, while fixed bed reactors are warming up to 300 DEG C~400 DEG C, and constant temperature 12h is until fischer-tropsch catalysts fully restore；
(2) fixed bed reactors temperature is reduced to 150 DEG C, is passed through unstripped gas and enters fixed bed reactors, control gas
Air speed is 1500~3000mL/gh, and adjusts fixed bed reactors pressure to 3.0~4.0MPa, improves fixed bed reactors
Temperature makes unstripped gas react in composite catalyst bed to 280 DEG C~320 DEG C；
(3) after step (2) reaction, from the condenser discharge product liquid in fixed bed reactors and incoagulable gas production
Object, incoagulable gas product are the residual raw materials gas for not participating in reaction, and product liquid is layered after standing and obtains oil phase and water phase, oil
It is mutually liquid hydrocarbon.The long chain hydrocarbons that the present invention generates can finally obtain gasoline, lubricating oil etc., the tail of system through down stream processing steps
Gas unreacted unstripped gas after further separation is recycled into fixed bed reactors.
Embodiment 1：
Coupling and catalyzing system uses zeolite oligomerization catalyst HZSM-5 and fischer-tropsch catalysts FeMn in the present embodiment, wherein
HZSM-5 be commercially available microporous molecular sieve catalyst, wherein m (Si):M (Al)=20:1, HZSM-5 is roasted and pressed by 550 DEG C
After piece sieving, the finished granule for obtaining 40~60 mesh (i.e. grain size is 0.25~0.38mm) is spare.
FeMn catalyst (m (Fe):M (Mn)=2:1) it is prepared by coprecipitation, specific preparation process is as follows：By Fe
(NO3)3·9H2O and Mn (NO3)2It is dissolved in deionized water, stirring to formation uniform solution, the mass ratio of wherein Fe and Mn are
2:1；Heated solution is to 80 DEG C and keeps this temperature, and being then slowly dropped into mass fraction dropwise under conditions of being vigorously stirred is
25% ammonia spirit, until the pH of solution is 8.0.As the addition solution of ammonium hydroxide generates crineous precipitation, treat that crineous precipitates
Aging 12h is stood after completely, the processes such as is then filtered, washed, dried, calcine and pulverized and sieved, finally obtain 40~60
Purpose FeMn particles are spare.
By the mass mixings such as HZSM-5 particles and the FeMn particles prepared and planetary ball mill ball milling 2h is put into, is obtained
Composite catalyst powder, granulation obtain the composite catalyst particle of 40~60 mesh, by 1g composite catalysts particle and the stone of 1g
Sand mixed packing enters fixed bed reaction pipe.
Coupling catalytic reactions：The prereduction of coupling and catalyzing system is in synthesis gas H2Molar ratio with CO is 1:Under 1 atmosphere
It carries out, pressure 0.1MPa, synthesis gas air speed 3000mL/gh, 300 DEG C of temperature, restores 12h.Reactor feed gas uses similar raw
The simulation gaseous mixture for the rich olefins synthesis gas that object oil catalytic pyrolysis generates, gas composition are as follows：The volume ratio of each composition gas
For C3H6/CO/H2/N2=20/30/10/40, reaction condition be 280 DEG C, pressure 4.0MPa of temperature, unstripped gas air speed 3000mL/
g·h.Product liquid is collected with 0 DEG C of condensation storage tank after reaction, product liquid is layered after standing and obtains oil phase and water phase, and water phase is
Water, oil phase are the oil-phase product that liquid hydrocarbon obtains, and are detected through GC-MS and analyze statistical result.Its concrete outcome is shown in Table 1, table 1
For the yield of Examples 1 to 8 catalyst coupled mode, reaction condition and product and C5+ selectivity comparing results.
Due to combination of the mechanical milling process to the destruction of molecular sieve catalyst and two kinds of active sites too closely, lead to raw material
Gas alkene acutely adds hydrogen, final product C5+Yield only about 4g/ (kgcata*h), C5+Selectivity only about 6%.
Embodiment 2：
Catalyst：The preparation method is the same as that of Example 1 by HZSM-5 and FeMn, by etc. quality two kinds of catalyst fines stirring
Mortar grinder is uniformly mixed, and obtained composite catalyst granulating powders obtain the particle of 40~60 mesh, by the 1g composite catalysts
The quartz sand mixed packing of particle and 1g enter fixed bed reaction pipe.
Coupling catalytic reactions：The prereduction of coupling and catalyzing system is in synthesis gas H2Molar ratio with CO is 1:Under 1 atmosphere
It carries out, pressure 0.1MPa, synthesis gas air speed 3000mL/gh, 300 DEG C of temperature, restores 12h.Reactor feed gas uses similar raw
The simulation gaseous mixture for the rich olefins synthesis gas that object oil catalytic pyrolysis generates, gas composition are as follows：The volume ratio of each composition gas
For C3H6/CO/H2/N2=20/30/10/40, reaction condition be 280 DEG C, pressure 4.0MPa of temperature, unstripped gas air speed 3000mL/
g·h.Product liquid is collected with 0 DEG C of condensation storage tank after reaction, product liquid is layered after standing and obtains oil phase and water phase, and water phase is
Water, oil phase are the oil-phase product that liquid hydrocarbon obtains, and are detected through GC-MS and analyze statistical result.Its concrete outcome is shown in Table 1, table 1
Yield and C for Examples 1 to 8 catalyst coupled mode, reaction condition and product5+Selective comparing result.
Final product C5+Yield reach about 60g/ (kgcata*h), C5+Selectivity reach about 47%, C5+C in product5 -
C12Gasoline section selectivity is up to 93%, while olefine selective is up to 90%, isomery hydrocarbon-selective about 60%.
Embodiment 3：
Catalyst：The preparation method is the same as that of Example 1 by HZSM-5 and FeMn, quality 40~60 purpose, two kinds of catalyst particles such as general
Grain is uniformly mixed to get the composite catalyst particles of 40~60 mesh, and the 1g composite catalyst particles are mixed dress with the quartz sand of 1g
Insert fixed bed reaction pipe.
Coupling catalytic reactions：Reaction condition is same as Example 1, final product C5+Yield reach about 59g/ (kgcata*
H), C5+Selectivity reach about 52%, C5+C in product5 -C12Gasoline section selectivity is up to more than 95%, while olefine selective reaches
97%, isomery hydrocarbon-selective about 70%.Its concrete outcome is shown in Table 1, and table 1 is Examples 1 to 8 catalyst coupled mode, reaction item
The yield and C of part and product5+Selective comparing result.
Embodiment 4：
Catalyst：The preparation method is the same as that of Example 1 by HZSM-5 and FeMn, and the HZSM-5 of 40~60 mesh prepared is catalyzed
Agent particle and FeMn particles respectively with etc. the quartz sand of quality mix, Catalyst packing is catalyzed using upstream bed 0.5g FeMn
Agent, down stream are 0.5g HZSM-5 catalyst；Remaining is consistent.
Coupling catalytic reactions：Reaction condition is same as Example 1.Final product C5+Yield reach about 71g/ (kgcata*
H), C5+Selectivity reach about 59%, C5+C in product5 -C12Gasoline section selectivity is up to more than 95%, while olefine selective is about
96%, isomery hydrocarbon-selective about 67%.Its concrete outcome is shown in Table 1, and table 1 is Examples 1 to 8 catalyst coupled mode, reaction item
The yield and C of part and product5+Selective comparing result.
Embodiment 5：
Catalyst：The preparation method is the same as that of Example 1 by HZSM-5 and FeMn, and the HZSM-5 of 40~60 mesh prepared is catalyzed
Agent particle and FeMn particles respectively with etc. the quartz sand of quality mix, when Catalyst packing, is urged using down stream 0.5g FeMn
Agent, upstream bed 0.5g HZSM-5 catalyst, centre is with suitable silica wool interval.
Coupling catalytic reactions：Reaction condition is same as Example 1.Final product C5+Yield reach about 194g/
(kgcata*h), C5+Selectivity reach about 78%, C5+C in product5 -C12Gasoline section selectivity is up to more than 95%, while alkene
Selectivity is up to 97%, isomery hydrocarbon-selective about 80%.Its concrete outcome is shown in Table 1, and table 1 is Examples 1 to 8 catalyst coupled mode
The yield and C of formula, reaction condition and product5+Selective comparing result.
Embodiment 6：
Catalyst：The preparation of HZSM-5 and FeMn and packing method are the same as embodiment 5.
Coupling catalytic reactions：Reaction condition is same as Example 1, and in addition to reaction pressure is 3.0MPa, other conditions are kept
Unanimously.Final product C5+Yield reach about 196g/ (kgcata*h), C5+Selectivity reach about 81%, C5+C in product5 -
C12Gasoline section selectivity is up to more than 95%, while olefine selective is up to 97%, isomery hydrocarbon-selective about 72%.Its concrete outcome is shown in
Table 1, table 1 are the yield and C of Examples 1 to 8 catalyst coupled mode, reaction condition and product5+Selective comparing result.
Embodiment 7：
Catalyst：The preparation of HZSM-5 and FeMn and packing method are the same as embodiment 5.
Coupling catalytic reactions：Reaction condition is same as Example 1, in addition to reaction pressure is 3.0MPa, reaction velocity is
1500mL/gh, other conditions are consistent.The yield of final product C5+ reaches about 169g/ (kgcata*h), C5+Selection
Property reaches about 83%, C5+C in product5 -C12Gasoline section selectivity is up to more than 95%, while olefine selective is up to 92%, isohydrocarbon
Selectivity about 78%.Its concrete outcome is shown in Table 1, and table 1 is the receipts of Examples 1 to 8 catalyst coupled mode, reaction condition and product
Rate and C5+Selective comparing result.
Embodiment 8：
Catalyst：The preparation of HZSM-5 and FeMn and packing method are the same as embodiment 5.
Coupling catalytic reactions：Reaction condition is same as Example 1, in addition to the prereduction of coupling and catalyzing system is in synthesis gas H2
Molar ratio with CO is 1:It is carried out under 1 atmosphere, temperature is 400 DEG C, restores 12h；Reaction temperature is 320 DEG C, and other conditions are protected
It holds consistent.Final product C5+Yield reach about 163.5g/ (kgcata*h), C5+Selectivity reach about 83%, C5+In product
C5 -C12Gasoline section selectivity is up to more than 95%, while olefine selective is up to 96%, isomery hydrocarbon-selective about 75%.It is specifically tied
Fruit is shown in Table 1, and table 1 is the yield and C of Examples 1 to 8 catalyst coupled mode, reaction condition and product5+Selectivity comparison knot
Fruit.
Table 1 is the yield and C of Examples 1 to 8 catalyst coupled mode, reaction condition and product5+Selectivity comparison knot
Fruit, as shown in table 1.
Table 1
It can be obtained by table 1：By Fischer-Tropsch-oligomerisation coupling and catalyzing can in successful conversion rich olefins synthesis gas effective alkene and
CO carbon sources generate liquid higher hydrocarbons, the coupling that ball milling mixing, mortar grinder mixing and granulation mass are mixed in the coupled modes of catalyst
The product yield and C that conjunction mode obtains5+The selectivity of liquid hydrocarbon is all not so good as the product that the coupled modes of dual bed landfill obtain
Yield and C5+The selectivity of liquid hydrocarbon.In addition to this, the coupled modes of Fischer-Tropsch show higher reactivity after first oligomerisation
With liquid hydrocarbon-selective, while relatively low reaction velocity be conducive to improve C5+Liquid hydrocarbon master is obtained by the reaction in the selectivity of liquid hydrocarbon
To be C5 -C12The isomerizing olefins of distribution, the optimal olefin ratios of product are more than 90%, and isomerisation degree is more than 60%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification etc.
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the method that a kind of Fischer-Tropsch-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon, which is characterized in that including
Following steps：
Unstripped gas is passed through to progress Fischer-Tropsch-oligomerisation coupling catalytic reactions in the fixed bed reactors for be mounted with composite catalyst, production
The raw liquid mixture comprising liquid hydrocarbon and water, stratification obtain upper oil phase i.e. liquid hydrocarbon；
The composite catalyst is fischer-tropsch catalysts and the coupled catalyst of catalyst for oligomerization.
2. the method that Fischer-Tropsch according to claim 1-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon,
It is characterized in that, specifically comprise the following steps：
(1) composite catalyst is loaded in fixed bed reactors, replaces synthesis gas at room temperature until empty in fixed bed reactors
After gas is synthesized gas displacement completely, normal pressure is passed through synthesis gas, while fixed bed reactors are warming up to 300 DEG C~400 DEG C, and constant temperature
12h is until fischer-tropsch catalysts fully restore；
(2) fixed bed reactors temperature is reduced to 150 DEG C, is passed through unstripped gas and enters fixed bed reactors, control gas space velocity
For 1500~3000mL/gh, and fixed bed reactors pressure is adjusted to 3.0~4.0MPa, improve fixed bed reactors temperature
To 280 DEG C~320 DEG C, unstripped gas is made to react in composite catalyst bed；
(3) after step (2) reaction, product liquid and incoagulable gas product are discharged from the condenser in fixed bed reactors,
Incoagulable gas product is the residual raw materials gas for not participating in reaction, and product liquid is layered after standing and obtains oil phase and water phase, oil phase
For liquid hydrocarbon.
3. Fischer-Tropsch according to claim 1 or 2-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares the side of liquid hydrocarbon
Method, which is characterized in that the unstripped gas is rich olefins synthesis gas, and the rich olefins synthesis gas includes C2-4Alkene and H2,CO
Gaseous mixture.
4. Fischer-Tropsch according to claim 1 or 2-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares the side of liquid hydrocarbon
Method, which is characterized in that the coupled mode of the composite catalyst is ball milling mixing, mortar grinder mixes, particle mixing or double
Bed loads.
5. the method that Fischer-Tropsch according to claim 4-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon,
It is characterized in that, the coupled mode of the coupling and catalyzing system is loaded for dual bed.
6. Fischer-Tropsch according to claim 1 or 2-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares the side of liquid hydrocarbon
Method, which is characterized in that the active metal component of the fischer-tropsch catalysts be Fe or Co, catalyst for oligomerization for Si-Al molecular sieve,
Solid phosphoric acid or nickel metal oxide catalyst.
7. the method that Fischer-Tropsch according to claim 6-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon,
It is characterized in that, the fischer-tropsch catalysts are FeMn catalyst, catalyst for oligomerization is HZSM-5 catalyst.
8. the method that Fischer-Tropsch according to claim 7-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon,
It is characterized in that, the FeMn catalyst is prepared by coprecipitation, specific preparation process is as follows：By Fe (NO3)3·
9H2O and Mn (NO3)2It is dissolved in deionized water, stirring to formation uniform solution, the mass ratio of wherein Fe and Mn are 2:1；By institute
The solution stated is heated to 80 DEG C of constant temperature, then under conditions of stirring, instills ammonia spirit dropwise into solution, adjusts solution
PH is 8.0, treats to generate crineous precipitation in solution, and crineous precipitation is completely rear to stand 12h, and obtained crineous is precipitated and is carried out
Post processing, finally obtains FeMn catalyst.
9. the method that Fischer-Tropsch according to claim 2-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares liquid hydrocarbon,
It is characterized in that, H in synthesis gas described in step (1)2Molar ratio with CO is 1.
10. Fischer-Tropsch according to claim 2-oligomerisation coupling and catalyzing conversion rich olefins synthesis gas prepares the side of liquid hydrocarbon
Method, which is characterized in that the reaction condition described in step (2) is：280 DEG C, reaction pressure 3.0MPa, air speed 1500mL/g of temperature
h。
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