CN107824214A - A kind of method of synthesis gas preparing low-carbon olefins - Google Patents
A kind of method of synthesis gas preparing low-carbon olefins Download PDFInfo
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- CN107824214A CN107824214A CN201711106883.4A CN201711106883A CN107824214A CN 107824214 A CN107824214 A CN 107824214A CN 201711106883 A CN201711106883 A CN 201711106883A CN 107824214 A CN107824214 A CN 107824214A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 58
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000047 product Substances 0.000 claims abstract description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 230000001186 cumulative effect Effects 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 70
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003245 coal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002028 Biomass Substances 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- -1 propylene, butylene Chemical group 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000001588 bifunctional effect Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 230000037351 starvation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a kind of method of synthesis gas preparing low-carbon olefins.Method is：Make synthesis gas that F- T synthesis cracking reaction occur in the presence of multifunction catalyst, reaction temperature is 250 400 DEG C, and reaction pressure is 0 5MPa, and unstripped gas cumulative volume air speed is 1000 10000h‑1, then low-carbon alkene is isolated from reaction product.Multifunction catalyst mainly includes following component：By weight, Fe2O310 60%, MnO 0.5 20%, K2O 0.5 10% and Al2O310 30%, remaining is molecular sieve.Fischer-Tropsch synthesis and cracking reaction can occur simultaneously for the present invention, solve the problems, such as that selectivity of light olefin is low in the prior art, and technological operation flexibility is high, can according to ethene, propylene, butylene market conditions, reasonable adjusting product is distributed within the specific limits, has the characteristics of simple to operate, synergy is obvious.
Description
Technical field
The present invention relates to chemical technology field, more particularly, to a kind of method of synthesis gas preparing low-carbon olefins.
Background technology
Alkene is important industrial chemicals, occupies very important status in national economy, and ethene, propylene and butylene
It is the basic material of all kinds of chemical products such as synthetic plastic, fiber Deng low-carbon alkene.With the development of chemical industry, low-carbon alkene
Demand it is more and more big.So far, the approach of the low-carbon alkene such as preparing ethylene, propylene is mainly by light oil cracking process,
With the increasingly depleted of petroleum resources in global range, following energy resource structure certainly will shift.Compared with petroleum resources, coal
With natural gas resource relative abundance, develop the low-carbon alkene production technology based on coal and natural gas and have great importance.From
The exploitation of synthesis gas (can be converted to by natural gas and coal) directly preparing ethylene, propylene technology, can not only reduce and oil is provided
The dependence in source, and to some chemical industrial expansion important in inhibiting in rich coal oil starvation area.The characteristics of China's energy is rich
Coal, few gas oil starvation, develop the process for being converted into oil product through synthesis gas by coal/natural gas, it is right on the energy not only to reduce
External dependence, and have great importance for problem of environmental pollution caused by solution fire coal.
Synthesis gas alkene directly processed typically uses fischer-tropsch reaction (Fischer-Tropsch, FT) route, and fischer-tropsch reaction is
Nineteen twenty-three is invented by Germany scientist Frans Fischer and Hans Tropsch, and the research direction has become grinds in the recent period
One of focus studied carefully.Coal based synthetic gas FT synthesis oil-producing techniques achieve industrial applications in China, but FT is synthesized and is used for
Alkene processed, mainly face olefine selective raising and product distribution effective control the problems such as.It is because FT synthesizes alkene processed
Strong exothermal reaction, easily cause hot-spot and promote methanation and the generation of carbon dioxide and the generation of carbon distribution, reduce total
Olefin yields；In addition, alkene easily occurs secondary hydrogenation reaction and is converted into saturation as a kind of intermediate product in FT building-up processes
Alkane, so as to cause the selectivity of low-carbon alkene relatively low.
In view of this, it is special to propose the present invention.
The content of the invention
It is an object of the invention to provide a kind of method of synthesis gas preparing low-carbon olefins, described method can be sent out simultaneously
Raw Fischer-Tropsch synthesis and cracking reaction, solve the problems, such as that selectivity of light olefin is low in the prior art, and technological operation
Flexibility is high, can according to ethene, propylene, butylene market conditions, within the specific limits reasonable adjusting product be distributed, there is behaviour
Make the characteristics of simple, synergy is obvious.
In order to realize the above object the invention provides following technical scheme：
A kind of method of synthesis gas preparing low-carbon olefins, it is characterised in that comprise the following steps：
Make synthesis gas that F- T synthesis-cracking reaction, reaction temperature 250-400 occur under the catalysis of multifunction catalyst
DEG C, reaction pressure 0-5MPa, unstripped gas cumulative volume air speed is 1000-10000h-1, then low-carbon alkene is isolated from reaction product
Hydrocarbon；
The multifunction catalyst mainly includes following component：By weight,
Fe2O310-60%, MnO 0.5-20%, K2O 0.5-10% and Al2O310-30%, remaining is molecular sieve.
Multifunction catalyst used in the present invention has F- T synthesis and the dual-use function of catalytic cracking, and main presentation is following
Feature：
1st, the material that activity is played in catalyst is metal simple-substance or metal complex and molecular sieve, using preceding suitable
At a temperature of reduced.
2nd, metallic iron, other modified metals and molecular sieve collective effect can just improve the choosing of preparing low-carbon olefin
Selecting property.Wherein, molecular sieve is as solid acid catalyst, using its special pore passage structure (including between molecular skeleton, molecule
Build bridge the ring formed, the level such as cage) show higher inner ratio surface area, good heat endurance, to small-molecule starting material and small
Molecular product select type, can modulation acid centre the features such as, therefore reaction intermediate can be promoted to low molecule amount
Product converts, and then improves the probability of generation low-carbon alkene.
Therefore, when the present invention uses above multifunction catalyst preparing low-carbon olefins, the overall selectivity of C2-C4 low-carbon alkenes
Can reach more than 50%, (overall selectivity of C2-C4 low-carbon alkenes refers to：Be converted into low-carbon alkene CO reacting doses divided by CO it is total anti-
It should measure and subtract CO2Growing amount).
Above method can also further optimize, such as：
Preferably, the molecular sieve is one or more mixing in ZSM-5, ZSM-11, SPAO-34, preferably ZSM-5 and
One or both of SPAO-34 is mixed.
The internal microstructure of ZSM-5, ZSM-11 and SPAO-34 molecular sieve is to low molecule organic matter (especially low molecule
Alkene) select that type effect is more obvious, and then improve the selectivity of low-carbon alkene, these three both can be used alone, can also
It is used in mixed way, preferably one or both of ZSM-5 and SPAO-34 are mixed.
The silica alumina ratio of above molecular sieve is arbitrary in principle, but difference is distributed with the product of different silica alumina ratios catalysis generation
It is different, for the purpose of high yield low-carbon alkene, preferably following silica alumina ratio：
Preferably, the silica alumina ratio of the ZSM-5 is 30-500, for example, 30,50,100,150,200,250,300,350,
400th, between 450,500 etc., preferably 100-300, or 200-300.
Preferably, the silica alumina ratio of the SPAO-34 is 0.01-1, for example, 0.01,0.05,0.1,0.2,0.3,0.5,0.7,
0.8th, 0.9,1 etc., preferably 0.1-0.5.
Preferably, in multifunction catalyst, by weight, Fe2O325-50%, MnO 2-10%, K2O 1-5% and
Al2O315-25%, remaining is molecular sieve；It is higher using selectivity of light olefin during the catalyst.
It is highly preferred that in multifunction catalyst, Fe2O335-45%, MnO 6-8%, K2O 3-4% and Al2O3 20-
25%, remaining is molecular sieve.
Multifunction catalyst provided by the present invention can use any means to prepare, such as infusion process, the precipitation method, ion are handed over
Change method, spraying process, blending method etc., as long as meeting composition in final products as described above, wherein, using the precipitation method as
It is excellent, it is specific as follows the step of the precipitation method：
1st, using coprecipitation, Fe base catalyst is prepared first.Ferric nitrate is configured to mix by a certain percentage with manganese nitrate
Close salting liquid.
2nd, solution of potassium carbonate is configured as precipitating reagent.
3rd, under the conditions of 20-90 DEG C, mixed salt solution is added dropwise together with precipitating reagent, maintains pH=6-13, is carried out
Coprecipitation process.
4th, sediment is subjected to centrifuge washing, then in 40-100 DEG C of drying.
5th, the sample of drying is calcined 2-5h at 400-600 DEG C, obtains Fe base catalyst.
6th, ZSM-5, ZSM-11 or SAPO-34 molecular sieve of different silica alumina ratios are subjected to alkali process, hydro-thermal process, acid treatment
Etc. one or more of modified methods, multi-stage artery structure is made it have.
7th, by Fe bases catalyst and ZSM-5, ZSM-11 or SAPO-34 the molecular sieve one or more being modified according to certain
Ratio is mixed, then extruded moulding, obtains multifunction catalyst.
Compared to other methods, the precipitation method have the advantages that preparation method is simple, each component is well mixed.
Preferably, the temperature of the Fischer-Tropsch-cracking synthetic reaction is 280-350 DEG C, reaction pressure 0.2-2MPa, raw material
Gas cumulative volume air speed is 1500-6000h-1。
Compared to traditional Fischer-Tropsch synthesis, reaction velocity of the invention is higher, and treating capacity is bigger, and this is to a certain extent
Also improve production efficiency.
In above method, H in the synthesis gas2Volume ratio with CO is preferably 0.5~5:1, it is higher comprehensive to obtain
Conjunction benefit, more preferably 1~3:1.
Synthesis gas of the present invention can be by coal, natural gas, biomass, shale gas, coal bed gas and oven gas
In one or more of combination conversions obtain.The synthesis gas of existing commercial syngas fabrication process, may be applicable to
The technique of the present invention, H in synthesis gas2Total amount (volume) with CO is generally more than 80%.
Separation of the present invention can use arbitrary separation method, such as conventional gas-liquid separator, carbon monoxide, two
After gas separator separates, unreacted hydrogen and carbon monoxide reenter reaction for carbonoxide, hydrogen and C1-C4 lighter hydrocarbons
Device reacts, and low-carbon alkene, low-carbon alkanes and carbon dioxide separate collection；Part or all of freshening weight of the oil phase such as C5+ part
Newly enter reactor reaction, another part is separated into gasoline, diesel oil and heavy oil through liquid phase separator, and low-carbon is further improved with this
Olefins yield.
The above method of the present invention can be carried out in arbitrary reactor, such as fixed bed reactors, slurry reactor
Device, moving-burden bed reactor or fluidized-bed reactor, preferably fluidized-bed reactor.
Multifunction catalyst is activated in addition, can also first be passed through hydrogen before reactions, led to preferably at 350 DEG C
Enter 5h to be activated.
To sum up, compared with prior art, invention achieves following technique effect：
(1) method of synthesis gas preparing low-carbon olefins of the present invention employs a kind of multifunction catalyst, it is possible to achieve low-carbon
The benefit of alkene high yield；
(2) present invention can effectively adjust low-carbon alkene by adjusting the reaction condition of preparing low-carbon olefin
Distribution, and then select the production line of maximization of economic benefit；
(3) present invention can effectively control the selectivity of low-carbon alkanes；By adopting the freshening of C5+ cuts, entering one
Step improves the selectivity of low-carbon alkene it is also possible to which effective controlling reaction temperature, realization reduce energy consumption while taking heat.
(4) reaction condition of the invention is relatively mild, and reaction temperature is easily controllable, can effectively reduce running cost, realizes
Maximizing the benefits.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the process chart that the embodiment of the present invention 1 provides.
Embodiment
Technical scheme is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that following described embodiment is part of the embodiment of the present invention, it is rather than whole
Embodiment, the present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, ability
The every other embodiment that domain those of ordinary skill is obtained under the premise of creative work is not made, belongs to guarantor of the present invention
The scope of shield.Unreceipted actual conditions person in embodiment, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same
Or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O335%th, MnO 6%, K2O 4%, Al2O320%th, ZSM-5 molecular sieve 35%, the sial of ZSM-5 molecular sieve
Than for 300.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 320 DEG C, pressure 0.5MPa, and the total air speed of unstripped gas is
1000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 2
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O335%th, MnO 6%, K2O 4%, Al2O320%th, SPAO-34 molecular sieves 35%, SPAO-34 molecular sieves
Silica alumina ratio is 0.1.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 320 DEG C, pressure 0.5MPa, and the total air speed of unstripped gas is
1000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 3
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O335%th, MnO 6%, K2O 4%, Al2O320%th, ZSM-5 molecular sieve 35%, the sial of ZSM-5 molecular sieve
Than for 100.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 3, and reaction temperature is 350 DEG C, pressure 1.0MPa, and the total air speed of unstripped gas is
3000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 4
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O335%th, MnO 6%, K2O 4%, Al2O320%th, ZSM-5 molecular sieve 35%, the sial of ZSM-5 molecular sieve
Than for 200.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 280 DEG C, pressure 0.5MPa, and the total air speed of unstripped gas is
2000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/3 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 5
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O335%th, MnO 6%, K2O 4%, Al2O320%th, ZSM-5 molecular sieve 35%, the sial of ZSM-5 molecular sieve
Than for 300.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 300 DEG C, pressure 2.0MPa, and the total air speed of unstripped gas is
2500h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 6
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O325%th, MnO 4%, K2O 3%, Al2O325%th, SPAO-34 molecular sieves 43%, SPAO-34 molecular sieves
Silica alumina ratio is 0.5.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 320 DEG C, pressure 0.5MPa, and the total air speed of unstripped gas is
2000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 7
Present embodiments provide a kind of bifunctional catalyst of the direct producing light olefins of synthesis gas, the weight hundred of its each component
Point ratio is:Fe2O345%th, MnO 8%, K2O 4%, Al2O320%th, SPAO-34 molecular sieves 23%, SPAO-34 molecular sieves
Silica alumina ratio is 0.1.
The present embodiment additionally provides a kind of technique of the direct producing light olefins of synthesis gas, and its flow is as shown in figure 1, its technique
Condition is as follows：H in synthesis gas2/ CO volume ratios are 2, and reaction temperature is 320 DEG C, pressure 0.5MPa, and the total air speed of unstripped gas is
2000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+1/2 freshening of cut, obtained after gaseous product separation
Low-carbon alkene, reaction result are shown in Table 1.
Embodiment 8
It is that reaction condition is different from the main distinction of embodiment 2, the H in synthesis gas2/ CO volume ratios are 5, reaction temperature
For 400 DEG C, pressure 5MPa, the total air speed of unstripped gas is 6000h-1, by oil-phase product C5 after the reacted device Reaction Separation of synthesis gas+
1/2 freshening of cut, low-carbon alkene is obtained after gaseous product separation, reaction result is shown in Table 1.
The preparation method of the catalyst of above example 1 to 8 of the present invention is identical, as follows：
1st, using coprecipitation, Fe base catalyst is prepared first.Ferric nitrate is configured to mix by a certain percentage with manganese nitrate
Close salting liquid.
2nd, solution of potassium carbonate is configured as precipitating reagent.
3rd, under the conditions of 20-90 DEG C, mixed salt solution is added dropwise together with precipitating reagent, maintains pH=6-13, is carried out
Coprecipitation process.
4th, sediment is subjected to centrifuge washing, then in 40-100 DEG C of drying.
5th, the sample of drying is calcined 2-5h at 400-600 DEG C, obtains Fe base catalyst.
6th, ZSM-5, ZSM-11 or SAPO-34 equimoleculars of different silica alumina ratios sieve is subjected to alkali process, hydro-thermal process, at acid
One or more of modified methods such as reason, make it have multi-stage artery structure.
7th, by Fe bases catalyst and ZSM-5, ZSM-11 or SAPO-34 the molecular sieve one or more being modified according to certain
Ratio is mixed, then extruded moulding, obtains multifunction catalyst.
Comparative example 1
It is different from the composition that the main distinction of embodiment 2 is catalyst, the preparation of catalyst and course of reaction and condition
It is same as Example 2.Al is free of in the catalyst of the comparative example2O3, it is specially：By weight percentage, Fe2O360%th, MnO
8%th, K2O 4%, SPAO-34 molecular sieves 43%, the silica alumina ratio of SPAO-34 molecular sieves is 0.1.Reaction result is shown in Table 1.
Comparative example 2
It is different from the composition that the main distinction of embodiment 2 is catalyst, preparation, course of reaction and the condition of catalyst with
Embodiment 2 is identical.Molecular sieve is replaced with activated carbon by the catalyst of the comparative example, is specially：By weight percentage,
Fe2O360%th, MnO 8%, K2O 4%, activated carbon 43%.Reaction result is shown in Table 1.
Comparative example 3
It is C5 with the main distinction of embodiment 2+Freshening, catalyst and reaction condition be not same as Example 2 for cut.
The technology assessment result of table 1
Note：In table 1, each data are calculated by below equation, are calculated by the amount of material.
CO conversion ratios=(CO inlet-CO quantums of output)/CO inlets；
CnHmSelectivity=nCnHm/ (CO inlet-CO quantums of output-CO2Quantum of output), CO is not calculated generally2。
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
- A kind of 1. method of synthesis gas preparing low-carbon olefins, it is characterised in that comprise the following steps：Make synthesis gas that F- T synthesis-cracking reaction occur under the catalysis of multifunction catalyst, reaction temperature is 250-400 DEG C, Reaction pressure is 0-5MPa, and unstripped gas cumulative volume air speed is 1000-10000h-1, then low-carbon alkene is isolated from reaction product；The multifunction catalyst mainly includes following component：By weight,Fe2O310-60%, MnO 0.5-20%, K2O 0.5-10% and Al2O310-30%, remaining is molecular sieve.
- 2. according to the method for claim 1, it is characterised in that the molecular sieve is in ZSM-5, ZSM-11, SPAO-34 One or more mixing, preferably one or both of ZSM-5 and SPAO-34 mix.
- 3. according to the method for claim 2, it is characterised in that the silica alumina ratio of the ZSM-5 is 30-500, preferably 100- 300；The silica alumina ratio of the SPAO-34 is 0.01-1, preferably 0.1-0.5.
- 4. according to the method described in claim any one of 1-3, it is characterised in that the multifunction catalyst is mainly comprising following Composition：By weight, Fe2O325-50%, MnO 2-10%, K2O 1-5% and Al2O315-25%, remaining is molecular sieve.
- 5. according to the method described in claim any one of 1-3, it is characterised in that the multifunction catalyst is mainly comprising following Composition：By weight, Fe2O335-45%, MnO 6-8%, K2O 3-4% and Al2O320-25%, remaining is molecular sieve.
- 6. the method for synthesis gas preparing low-carbon olefins according to claim 1, it is characterised in that the F- T synthesis-split The temperature of solution reaction is 280-350 DEG C, reaction pressure 0.2-2MPa, and unstripped gas cumulative volume air speed is 1500-6000h-1。
- 7. according to the method for claim 1, it is characterised in that H in the synthesis gas2Volume ratio with CO is 0.5~5:1, It is preferred that 1~3:1.
- 8. the method according to claim 1 or 7, it is characterised in that H in the synthesis gas2Cumulative volume accounting with CO is More than 80%.
- 9. according to the method for claim 1, it is characterised in that also by oil-phase product C5 after the separation+Cut is whole Or part freshening, preferably by oil-phase product C5+At least half freshening of cut；Before the F- T synthesis-cracking reaction, first it is passed through hydrogen and the multifunction catalyst is entered at 350~400 DEG C Row activation.
- 10. according to the method for claim 1, it is characterised in that the synthesis gas is by coal, natural gas, biomass, shale What one or more of combination conversions in gas, coal bed gas and oven gas obtained.
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