CN101993707B - Fischer-Tropsch synthesis method for heavy hydrocarbon - Google Patents
Fischer-Tropsch synthesis method for heavy hydrocarbon Download PDFInfo
- Publication number
- CN101993707B CN101993707B CN200910057795.9A CN200910057795A CN101993707B CN 101993707 B CN101993707 B CN 101993707B CN 200910057795 A CN200910057795 A CN 200910057795A CN 101993707 B CN101993707 B CN 101993707B
- Authority
- CN
- China
- Prior art keywords
- fischer
- heavy hydrocarbon
- tropsch synthesis
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a Fischer-Tropsch synthesis method for heavy hydrocarbon, mainly solving the problems that as the Fischer-Tropsch synthesis reaction is an exothermal reaction, in the prior art, when a fixed bed is used, heat is difficultly removed for reaction and the temperature is easy to run away so that a catalyst is easy to inactivate; and when a fluidized bed is used, the selectivity of the heavy hydrocarbon is low. In the Fischer-Tropsch synthesis method, a synthesized gas is taken as a raw material; and the raw material is contacted and reacted with a fluidized bed catalyst at the conditions of 0.5-10MPa of pressure, 200-600 DEG C of reaction temperature and 100-8000 h<-1> of reaction air speed, so as to generate the heavy hydrocarbon, wherein the used iron-based fluidized bed catalyst takes at least one oxide selected from Si or Al as a carrier; and an active component contains a composition having the chemical formula based on an atom ratio as follows: Fe100AaBbCcOx, wherein A is selected from at least one of alkali metals or alkaline-earth metals, B is selected from at least one of La or Ce, and C is selected from at least one of Cu or Mn. By using the technical scheme of the method, the problems can be better solved. The method can be used in industrial production of Fischer-Tropsch synthesis reaction.
Description
Technical field
The present invention relates to the method for Fischer-Tropsch synthesis of heavy hydrocarbon.
Background technology
The method that synthetic gas is converted into liquid hydrocarbon through catalyst action is that nineteen twenty-three is by Germany scientist Frans Fischer and Hans Tropsch invention, be called for short F-T synthetic, be that heterogeneous catalysis hydrogenation occurs CO on metal catalyst, generate that to take straight-chain paraffin and alkene be the process of main mixture.Germany has just carried out research and development in the twenties in last century, and in 1936, has realized industrialization, after World War II because closing with petroleum industry competition economically; South Africa has abundant coal resources, but petroleum resources plaque is weary, and be subject to for a long time the restriction of international community's economy and political sanction, force its Development of Coal oils preparation industry technology, and in 1955, to have built up First throughput be the coal-based F-T synthetic oil factory (Sasol-1) in ten thousand tons of product/years of 25-40.
Twice world oil crisis of 1973 and 1979, causes world's crude oil price to fall and swings fluctuating, big rise and big fall, the consideration based on Strategic Technology deposit, and F-T synthetic technology is aroused the interest of industrialized country again.1980 and nineteen eighty-two, two the coal-based synthetic oil factories that in succession build up again and gone into operation of South Africa Sasol company.But plummeting of World oil price in 1986, has postponed F-T synthetic technology in other national heavy industrialization process.
Twentieth century is since the nineties, and petroleum resources are shortage and in poor quality increasingly, and coal and Sweet natural gas proven reserve but constantly increase simultaneously, and GTL technology causes extensive concern again.Through the development of decades, Fischer-Tropsch catalyst has also obtained significant progress, and conventional catalyzer is at present divided into two large classes active ingredient: ferrum-based catalyst and cobalt-base catalyst.According to the difference of the difference of adopted catalyzer and target product, Fischer-Tropsch synthesis device is divided into again fixed-bed reactor, fluidized-bed reactor and paste state bed reactor.Fixed-bed reactor complex structure, expensive, remove heat difficulty, the production capacity of whole device is lower.The feature of slurry state bed is that temperature of reaction is lower, be easy to control, but transformation efficiency is lower, and the liquid-solid separation that product mostly is slurries in high-carbon hydrocarbon and reactor is comparatively difficult.The feature of fluidized-bed reactor is that temperature is higher, and transformation efficiency is higher, does not have the difficulty of liquid-solid separation, and product mostly is lower carbon number hydrocarbons; Construction and process cost are lower, and low pressure reduction has been saved a large amount of compression expenses, and are more conducive to except the heat of emitting in dereaction, and simultaneously because gas line speed is low, wear problem is less, and this makes long-term operation become possibility.
Iron catalyst has advantages of a lot, as highly selective obtains low-carbon alkene, prepares high-octane gasoline etc., and ferrum-based catalyst also has the feature that operational condition is wide, product adjustability is large in addition.The preparation method of Fe-series catalyst mainly contains three kinds: the precipitator method (precipitated catalyst), sintering process (sintered catalyst) and oxide compound hybrid system (fused iron catalyst).The currently reported synthetic molten iron type that the mostly is catalyzer of fluidized-bed Fischer-Tropsch that is applied to, as a kind of for the synthetic molten iron type catalyzer of Fischer-Tropsch in mentioned in patent CN1704161A, catalyzer by the oxide compound of Fe, Al, K, Ca and on a small quantity other oxide compound form, 280 ℃ of temperature of reaction, reaction pressure 6.0MPa, catalyst loading 500 hours
-1, proportioning raw materials (mole) H
2under the condition of/CO=1.5, CO transformation efficiency is that the selectivity of 93.4%, C5+ hydrocarbon is 60.2%.
Summary of the invention
Technical problem to be solved by this invention be in prior art because Fischer-Tropsch synthesis is strong exothermal reaction, while using fixed bed, heat difficulty is removed in reaction, easily temperature runaway, makes the easy inactivation of catalyzer; While using fluidized-bed, the problem that selectivity of product is low, provides a kind of method of new Fischer-Tropsch synthesis of heavy hydrocarbon.The method has reacting balance, and catalyzer is difficult for temperature runaway, the advantage that product heavy hydrocarbon selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of Fischer-Tropsch synthesis of heavy hydrocarbon, take synthetic gas as raw material, and at pressure, be 0.5～10MPa, temperature of reaction is 200～600 ℃, reaction velocity is 100～8000 hours
-1, unstripped gas H
2/ CO ratio is that under 0.1～5.0: 1 condition, raw material contacts with the iron-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is C5 and above hydro carbons; It is carrier that iron-based fluid catalyst used be take at least one oxide compound being selected from Si or Al, and active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Fe
100A
aB
bC
cO
x
In formula, A is selected from least one in basic metal or alkaline-earth metal;
B is selected from least one in La or Ce;
C is selected from least one in Cu or Mn;
The span of a is 0.1～10.0;
The span of b is 0～10.0; When C=Mn, b > 0;
The span of c is 5.0～60.0;
X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Carrier consumption is 30～70% of catalyst weight by weight percentage.
The value preferable range that the value preferable range that in technique scheme, the value preferable range of a is 1.0～8.0, b is 0.1～8.0, c is 10～50, and carrier consumption preferable range is 40～60% of catalyst weight by weight percentage.
The manufacture method of catalyzer of the present invention there is no particular requirement, can be undertaken by well-established law.First catalyzer each component is made to solution, then be mixed and made into slurry with carrier, the spray-dried microspheroidal that is shaped to, catalyzer is made in last roasting.The preparation of slurry is preferably undertaken by CN1005248C method.
The raw material of manufacturing catalyzer of the present invention is:
Iron nitrate or ferric sulfate for iron component in catalyzer.
The most handy its nitrate of all the other components, oxyhydroxide maybe can be decomposed into the salt of oxide compound.
Raw material as carrier silicon-dioxide can be used silicon sol, silicon gel or both mixtures.If with silicon sol, its quality will meet the requirement of CN1005248C.
Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but with centrifugal better, can guarantee that the catalyzer of making has good size-grade distribution.
The roasting of catalyzer can be divided into two stages and carry out: the decomposition of each element salt and high-temperature roasting in catalyzer.Catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Maturing temperature is 500～800 ℃, is preferably 550～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two stoving ovens, also can in a stove, be divided into two regions, also can in continous way rotary roasting furnace, complete simultaneously and decompose and roasting.In catalyst decomposes and roasting process, to pass into appropriate air, to generate Catalytic active phase.
The reductive condition of the catalyzer that the present invention makes: pressure is between 0.05～5MPa, is preferably 0.1～4MPa; Reducing gas can be used hydrogen, carbon monoxide or synthetic gas, while using synthetic gas, and its H
2/ CO ratio is 0.1～6.0, is preferably 0.2～6.0; The load of reducing gas is 100～8000 hours
-1, be preferably 500～6000 hours
-1; Reduction temperature is 200～600 ℃, is preferably 220～500 ℃; Recovery time is 1～100 hour, is preferably 6～72 hours.
The reaction conditions of the catalyzer that the present invention makes: pressure is between 0.5～10MPa, is preferably 1～8MPa; Temperature of reaction is 200～600 ℃, is preferably 220～500 ℃; Catalyst loading is 100～8000 hours
-1, be preferably 500～6000 hours
-1; Unstripped gas H
2/ CO, than for than being 0.1～5.0, is preferably 0.5～3.0.
Catalyzer of the present invention is used in fluidized-bed, can solve in prior art because Fischer-Tropsch synthesis is strong exothermal reaction, and while using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway makes the problem of the easy inactivation of catalyzer; The rare earth element of introducing in catalyzer is as catalyst adjuvant, promoted the dispersion of catalyst activity component at catalyst surface, thereby be conducive to improve activity and the stability of catalyzer, solved while using fluidized-bed the problem that heavy hydrocarbon selectivity is low simultaneously in the past.Use method of the present invention, 280 ℃ of temperature of reaction, reaction pressure 2.0MPa, catalyst loading 3000 hours
-1, proportioning raw materials (mole) H
2under the condition of/CO=2/1, carry out Fischer-Tropsch synthesis, CO transformation efficiency is 91.5%, and in reaction product, the selectivity of heavy hydrocarbon reaches 71.4%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated, and protection scope of the present invention is not subject to the restriction of these embodiment.
Embodiment
[embodiment 1]
After 1.85 grams of potassium hydroxide add 5 grams, water heating, dissolve, obtain material (A); 371.7 grams of iron nitrates, 55.0 grams of cupric nitrates are dissolved in 450 grams of 60～90 ℃ of hot water, obtain material (B); By 15.9 grams of lanthanum nitrates, add 40 grams, water, after heating for dissolving as material (C).
The silicon sol that is 40% with 687.5 gram weight concentration by material (A) mixes, under agitation add successively material (B) and (C), with ammoniacal liquor, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry, after fully stirring, obtain slurry, according to well-established law, the slurry of making is carried out in spray-dryer to framboid moulding, at internal diameter, be finally 89 millimeters, length is 1700 millimeters
rotary roasting furnace in 500 ℃ of roastings 2.0 hours, make and consist of:
40％Fe
100K
3.0La
6.0Cu
25.0O
x+60％SiO
2
Prepared catalyzer carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 2～4]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer that form, gained catalyzer numbering and composition are respectively:
1 40％Fe
100K
3.0La
6.0Cu
25.0O
x+60％SiO
2
2 45％Fe
100K
2.0La
3.0Ce
2.5Cu
20.0O
x+55％Al
2O
3
3 50％Fe
100K
1.0Cs
3.0Ce
4.5Cu
10.0Mn
8.0O
x+50％SiO
2
4 50％Fe
100Ca
4.5Ce
3.0Cu
45.0O
x+50％(70％SiO
2+30％Al
2O
3)
5 55％Fe
100Ca
3.0Mg
3.0La
2.0Mn
30.0O
x+45％SiO
2
6 60％Fe
100Na
2.0Mg
3.0Cu
50.0O
x+40％SiO
2
Prepared catalyzer carries out Fischer-Tropsch synthesis under following reaction conditions, the results are shown in Table 1.
[comparative example 1～2]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer that form, gained catalyzer numbering and composition are respectively:
7 40％Fe
100La
6.0Cu
25.0O
x+60％SiO
2
8 50％Fe
100K
4.0Mn
40.0O
x+50％SiO
2
9 50％Fe
100K
6.0O
x+50％SiO
2
Prepared catalyzer carries out Fischer-Tropsch synthesis under following reaction conditions, and result is also listed in table 1.
The reductive condition of above-described embodiment and comparative example is:
400 ℃ of temperature
Pressure 3.0MPa
100 grams of loaded catalysts
Catalyst loading 4000 hours
-1
Reducing gas H
2/ CO=2/1
24 hours recovery times
Reaction conditions is:
280 ℃ of temperature of reaction
Reaction pressure 2.0MPa
100 grams of loaded catalysts
Catalyst loading 3000 hours
-1
Proportioning raw materials (mole) H
2/ CO=2/1
The evaluation result of table 1 embodiment catalyzer
Wt is weight.
Claims (4)
1. a method for Fischer-Tropsch synthesis of heavy hydrocarbon, take synthetic gas as raw material, at pressure, is 0.5～10MPa, and temperature of reaction is 200～600 ℃, and reaction velocity is 100～8000 hours
-1, unstripped gas H
2/ CO ratio is that under 0.1～5.0: 1 condition, raw material contacts with the iron-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is C5 and above hydro carbons; It is carrier that iron-based fluid catalyst used be take at least one oxide compound being selected from Si or Al, and active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Fe
100A
aB
bC
cO
x
In formula, A is selected from Ca and Mg;
B is selected from La;
C is selected from Mn;
The span of a is 0.1～10.0;
The span of b is 0～10.0 and b > 0;
The span of c is 5.0～60.0;
X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Carrier consumption is 40～60% of catalyst weight by weight percentage.
2. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, the span that it is characterized in that a is 1.0～8.0.
3. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, the span that it is characterized in that b is 0.1～8.0.
4. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, the span that it is characterized in that c is 10～50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910057795.9A CN101993707B (en) | 2009-08-31 | 2009-08-31 | Fischer-Tropsch synthesis method for heavy hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910057795.9A CN101993707B (en) | 2009-08-31 | 2009-08-31 | Fischer-Tropsch synthesis method for heavy hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101993707A CN101993707A (en) | 2011-03-30 |
| CN101993707B true CN101993707B (en) | 2014-03-05 |
Family
ID=43784474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910057795.9A Active CN101993707B (en) | 2009-08-31 | 2009-08-31 | Fischer-Tropsch synthesis method for heavy hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101993707B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103418393B (en) * | 2012-05-16 | 2016-02-10 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of Fischer-Tropsch synthesis of heavy hydrocarbon |
| CN103521241A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for direct conversion from synthesis gas to low-carbon olefine and preparation method thereof |
| CN103666517A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis |
| CN103657675B (en) * | 2012-09-05 | 2016-01-13 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of microspheroidal iron-base fischer-tropsch synthesis |
| CN103773409B (en) * | 2012-10-25 | 2016-08-24 | 中国石油化工股份有限公司 | The method being the direct preparing low-carbon olefins of raw material with synthesis gas |
| CN103772087B (en) * | 2012-10-25 | 2016-12-21 | 中国石油化工股份有限公司 | The method of the direct preparing low-carbon olefins of synthesis gas |
| CN104148106B (en) * | 2013-05-16 | 2016-08-03 | 中国石油化工股份有限公司 | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof |
| CN104289226B (en) * | 2014-09-08 | 2016-07-06 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of multifunctional solid catalyst |
| CN104815659A (en) * | 2015-04-21 | 2015-08-05 | 中国科学院上海高等研究院 | Iron-based catalyst used for Fischer-Tropsch synthesis, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583259A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Micro-ball iron-based catalyst for Fischer-Tropsch synthesis and its preparation and use |
-
2009
- 2009-08-31 CN CN200910057795.9A patent/CN101993707B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583259A (en) * | 2004-06-11 | 2005-02-23 | 中国科学院山西煤炭化学研究所 | Micro-ball iron-based catalyst for Fischer-Tropsch synthesis and its preparation and use |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101993707A (en) | 2011-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101993707B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbon | |
| CN102371155B (en) | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method | |
| CN102453492B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbons | |
| CN103664447B (en) | The method of synthesis gas alkene processed | |
| CN102371154B (en) | Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof | |
| CN105363464B (en) | Catalyst of synthesis gas light hydrocarbon directly processed and preparation method thereof | |
| CN102041021B (en) | Method for synthesizing heavy hydrocarbon by fischer-tropsch | |
| CN105363458B (en) | Synthesize catalyst of light hydrocarbon and preparation method thereof | |
| CN105363463B (en) | Catalyst of synthesis gas light hydrocarbon and preparation method thereof | |
| CN103933989A (en) | Catalyst for synthesis of low carbon olefins and its preparation method | |
| CN106607036A (en) | Oxalate hydrogenation catalyst, preparation method and uses thereof | |
| CN102041020B (en) | Fluidized bed Tropsch synthesis method for heavy hydrocarbons | |
| CN105435803B (en) | Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof | |
| CN102039135B (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN106607051A (en) | Catalyst for one-step preparation of low-carbon olefin from synthetic gas and preparation method thereof | |
| CN103418393B (en) | The Catalysts and its preparation method of Fischer-Tropsch synthesis of heavy hydrocarbon | |
| CN103666517A (en) | Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis | |
| CN103657674A (en) | Iron-based catalyst for preparing olefin from synthesis gas, as well as method and application of catalyst | |
| CN103657676B (en) | Microspherical Fischer-Tropsch catalyst and its preparation method and application | |
| CN106607059A (en) | Fe-Mn-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of Fe-Mn-based catalyst | |
| CN103521238B (en) | Micro spherical Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN109647428A (en) | The ferrum-based catalyst of one-step method from syngas producing light olefins | |
| CN101993706A (en) | Method for tropsch synthesis of hydrocarbon containing five or more carbon atoms | |
| CN109651034A (en) | The method of one-step method from syngas production low-carbon alkene | |
| CN106607049B (en) | Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |