CN103666517A - Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis - Google Patents
Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis Download PDFInfo
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- CN103666517A CN103666517A CN201210325162.3A CN201210325162A CN103666517A CN 103666517 A CN103666517 A CN 103666517A CN 201210325162 A CN201210325162 A CN 201210325162A CN 103666517 A CN103666517 A CN 103666517A
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Abstract
The invention relates to a method for producing heavy hydrocarbons through Fischer-Tropsch synthesis, which mainly solves the problems that difficult heat removal and possibly caused temperature runaway during Fischer-Tropsch synthesis reaction can easily inactivate a catalyst when a fixed bed is used because the reaction is a strong exothermic one and the heavy hydrocarbon selectivity is low when a fluidized bed is used in the prior art. The technical scheme of the method comprises the following steps: by taking synthesis gases as raw materials, under the conditions that the pressure is 0.5-10 MPa, the reaction temperature is 200-600 DEG C, the reaction space velocity is 100-8000 h<-1> and the H2/CO ratio of the raw gases is (0.1-5.0):1, enabling the raw materials to be in contact with an iron-based fluidized bed catalyst in a fluidized bed, and reacting to generate heavy hydrocarbons (C5+ hydrocarbons), wherein the iron-based fluidized bed catalyst takes at least one of Si or Al oxide as a carrier; and based on the ratio of atoms contained in the active components, the chemical formula is Fe100AaBbCcDdOx. Thus, the problems are well solved; and the method can be used for industrial production of fluidized bed Fischer-Tropsch synthesis reaction.
Description
Technical field
The present invention relates to a kind of method of 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 is low, provides a kind of method of new Fischer-Tropsch synthesis of heavy hydrocarbon.The method fluidized-bed reactor, has the heat of removing fast, the advantage that heavy hydrocarbon selectivity is high.
For solving 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, H in unstripped gas
2/ CO mol ratio is that under 0.1～5.0 condition, raw material contacts with the iron-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon; Wherein, described iron-based fluid catalyst take be selected from the oxide compound of Si or Al at least one be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Fe
100A
aB
bC
cD
dO
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;
D is selected from least one in Cr, Mo, W, V or Zr;
The span of a is 0.1～10.0;
The span of b is 0～10.0;
The span of c is 5.0～60.0;
The span of d is 0. 1～15.0;
X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Carrier consumption is 30～70% of catalyst weight by weight percentage.
In technique scheme, the value preferable range of a is 1.0～8.0, the value preferable range of b is 0.1～8.0, the value preferable range that the value preferable range of c is 10～50, d is 1.0～10.0, and carrier consumption preferable range is 40～60% of catalyst weight by weight percentage.Described heavy hydrocarbon is hydro carbons more than C5.When C is Mn, b>0.One of D preferred version is for being selected from least one in Cr, Mo or W.Two of D preferred version is to be selected from least one in V or Zr.A preferred version is at least one being selected from K, Na, Cs or Mg.Pressure preferable range is 1～8MPa, and temperature of reaction preferable range is 200～500 ℃, and reaction velocity preferable range is 500～6000 hours
-1.H in unstripped gas
2/ CO mol ratio preferable range is 0.5～3.0.
The manufacture method of the catalyzer in the inventive method 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, finally makes catalyzer at 450-700 ℃ of roasting 0.5-5 hour.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 mol 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.
Because the present invention adopts fluidized-bed process, therefore solved in prior art because Fischer-Tropsch synthesis is strong exothermal reaction, while using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway makes the problem of the easy inactivation of catalyzer; Because the rare earth element of introducing is as catalyst adjuvant, promote the dispersion of catalyst activity component at catalyst surface in addition in catalyzer, thereby be conducive to improve the activity of catalyzer, solved when using fluidized-bed the problem that heavy hydrocarbon selectivity is low.Use method of the present invention, 200～600 ℃ of temperature of reaction, reaction pressure 0.5～10MPa, catalyst loading 100～8000 hours
-1, proportioning raw materials (mole) H
2under the condition of/CO=0.1～5.0:1, carry out Fischer-Tropsch synthesis, CO transformation efficiency can reach 91.5%, and in reaction product, the selectivity of heavy hydrocarbon can reach 69.9%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
After 1.53 grams of potassium hydroxide add 10 grams, water heating, dissolve, obtain material (A); 461.1 grams of iron nitrates, 81.88 grams of cupric nitrates, 4.56 chromium trioxides are dissolved in 500 grams of hot water, obtain material (B); By 8.2 grams of lanthanum nitrates, add 25 grams, water, after heating for dissolving as material (C).
The silicon sol that is 40% with 312.5 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 be in the rotary roasting furnace of 1700 millimeters (89 * 1700 millimeters of φ) in 500 ℃ of roastings 2.0 hours, make and consist of:
50%Fe
100K
2.0La
2.5Cu
30.0Cr
4.0O
x＋50%SiO
2。
Catalyzer.
Prepared catalyzer carries out at reductive condition:
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
Reduce, then carry out under the following conditions Fischer-Tropsch synthesis:
38 millimeters of fluidized-bed reactors of φ
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 experimental result of Fischer-Tropsch synthesis is listed in table 1.
[embodiment 2～8]
Adopt the catalyzer from [embodiment 1] essentially identical method preparation with different compositions, gained catalyzer numbering and composition are respectively:
Embodiment 1 50%Fe
100k
2.0la
2.5cu
30.0cr
4.0o
x+ 50%SiO
2
Embodiment 2 40%Fe
100na
2.0mg
3.0ce
4.0cu
35.0cr
5.0o
x+ 60%Al
2o
3
Embodiment 3 45%Fe
100ca
5.0la
3.0ce
2.0mn
20.0cr
6.0o
x+ 55% (50%SiO
2+ 50%Al
2o
3)
Embodiment 4 55%Fe
100k
6.0la
6.0cu
15.0mn
25.0mo
2.
0o
x+ 45% SiO
2
Embodiment 5 60%Fe
100na
2.0cs
3.0ce
5.0mn
10.0cr
1.0mo
8.0o
x+ 40%SiO
2
Embodiment 6 50%Fe
100mg
2.0ca
7.0la
2.0cu
20.0cr
2.50o
x+ 50%SiO
2
Embodiment 7 60%Fe
100k
3.0sr
1.0ce
6.0cu
18.0mn
40.0v
2.0o
x+ 40%Al
2o
3
Embodiment 8 40%Fe
100k
3.0mg
3.0la
7.0cu
30.0v
4.0zr
2.0o
x+ 60%SiO
2
Prepared catalyzer with [embodiment 1] the same terms under carry out Fischer-Tropsch synthesis, the results are shown in Table 1.
[comparative example 1～4]
Adopt the catalyzer from [embodiment 1] essentially identical method preparation with different compositions, gained catalyzer numbering and composition are respectively:
Comparative example 1 50%Fe
100la
5.0cu
25.0cr
4.
5o
x+ 50%SiO
2
Comparative example 2 50%Fe
100k
4.0cu4
0.0mo4
.0o
x+ 50%SiO
2
Comparative example 3 60%Fe
100k
4.0la
5.0co
7.
0o
x+ 40%SiO
2
Comparative example 4 60%Fe
100k
8.0la
1.0cu
50.
0o
x+ 40%SiO
2
Prepared catalyzer with [embodiment 1] the same terms under carry out Fischer-Tropsch synthesis, result is also listed in table 1.
Table 1
[embodiment 9]
By each step and the condition Preparation and evaluation catalyzer of [embodiment 1], just temperature of reaction is 250 ℃, and its appreciation condition is listed in table 2, and evaluation result is listed in table 3.
[embodiment 10～16]
By each step and the condition Preparation and evaluation catalyzer of [embodiment 1], just change a certain appreciation condition wherein, its appreciation condition is listed in table 2, and evaluation result is listed in table 3.
Table 2
Table 3
Claims (10)
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, H in unstripped gas
2/ CO mol ratio is that under 0.1～5.0 condition, raw material contacts with the iron-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon; Wherein, described iron-based fluid catalyst take be selected from the oxide compound of Si or Al at least one be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Fe
100A
aB
bC
cD
dO
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;
D is selected from least one in Cr, Mo, W, V or Zr;
The span of a is 0.1～10.0;
The span of b is 0～10.0;
The span of c is 5.0～60.0;
The span of d is 0. 1～15.0;
X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Carrier consumption is 30～70% of catalyst weight by weight percentage.
2. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, the span that the span that the span that the span that it is characterized in that a is 1.0～8.0, b is 0.1～8.0, c is 10～50, d is 1.0～10.0.
3. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that carrier consumption is 40～60% of catalyst weight by weight percentage.
4. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that described heavy hydrocarbon is hydro carbons more than C5.
5. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that when C is Mn b>0.
6. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that D is selected from least one in Cr, Mo or W.
7. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that D is selected from least one in V or Zr.
8. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that A is selected from least one in K, Na, Cs or Mg.
9. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that pressure is 1～8MPa, and temperature of reaction is 200～500 ℃, and reaction velocity is 500～6000 hours
-1.
10. the method for Fischer-Tropsch synthesis of heavy hydrocarbon according to claim 1, is characterized in that H in unstripped gas
2/ CO mol ratio is 0.5～3.0.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435803A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst |
| CN114643062A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
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| CN102041020A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Fluidized bed Tropsch synthesis method for heavy hydrocarbons |
| CN102371155A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Iron-based catalyst for Fischer-Tropsch synthesis of heavy hydrocarbon and its preparation method |
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| CN102041020A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Fluidized bed Tropsch synthesis method for heavy hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105435803A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst |
| CN105435803B (en) * | 2014-08-27 | 2018-04-06 | 中国石油化工股份有限公司 | Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof |
| CN114643062A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
| CN114643062B (en) * | 2020-12-18 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and application thereof |
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Application publication date: 20140326 |