CN102041020B - Fluidized bed Tropsch synthesis method for heavy hydrocarbons - Google Patents
Fluidized bed Tropsch synthesis method for heavy hydrocarbons Download PDFInfo
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- CN102041020B CN102041020B CN200910201618.3A CN200910201618A CN102041020B CN 102041020 B CN102041020 B CN 102041020B CN 200910201618 A CN200910201618 A CN 200910201618A CN 102041020 B CN102041020 B CN 102041020B
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Abstract
The invention relates to a Tropsch synthesis method for heavy hydrocarbons, which mainly solves the problems that the reaction heat dissipation is difficult, temperature runaway is easily caused and the catalyst is easily inactivated when a fixed bed is used and the selectivity of the heavy hydrocarbons is low when a fluidized bed is used in the prior art because the Tropsch synthesis reaction is strong heat generating reaction. Synthesis gas is used as a raw material; under the conditions that the reaction pressure is 0.5 to 10MPa, the reaction temperature is 200 to 600 DEG C, the reaction space velocity is 100 to 8,000 per hour and the H2/CO molar ratio of the raw material gas is 0.1-5.0: 1, the raw material is contacted with a cobalt-based fluidized bed catalyst in the fluidized bed and reacted to generate the heavy hydrocarbons, wherein the heavy hydrocarbons are hydrocarbons of over C5; and in the cobalt-based fluidized bed catalyst, at least one of oxides of Si and Al or mixture of Si or Al and ZrO2 is selected as a carrier, and the active ingredient contains the following compound with chemical formula in an atomic ratio: Co100AaBbOx, wherein in the formula, A is selected from at least one of alkali metals or alkaline earth metals, and B is selected from at least one of Cr, Ni, Cu and Zn. According to the technical scheme, the problems are well solved, and the method can be used in the industrial production of fluidized bed Tropsch synthesis reaction.
Description
Technical field
The present invention relates to a kind of method of fluidized-bed 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.
Cobalt-base catalyst is high owing to having per pass conversion, and the life-span is long, and straight chain hydrocarbon yield is high; Stable and be difficult for carbon distribution and poisoning in reaction process, the advantage such as in product, oxygenatedchemicals is few, and water gas shift reaction is insensitive; Main drawback has: expensive, catalyzer warm area is narrow, and adjustability is poor.Therefore, the Co base F-T catalyzer at present with prospects for commercial application is loading type substantially, or the mixture of Co and the formation of other metal oxide.CN1764499A report be applied to the synthetic cobalt-base catalyst of fluidized-bed Fischer-Tropsch, this catalyzer is selected from cobalt, nickel and ruthenium metal precursor compound by two or more is comprised is impregnated in the silicon-dioxide base carrier of alkali metal containing and/or alkaline-earth metal and prepares, at pressure 1MPa, 250 ℃ of temperature of reaction, catalyst loading 2000 hours
-1, unstripped gas H
2under the condition of/CO=2/1, CO transformation efficiency is 90% left and right, methane selectively 13% left and right, the chainpropagation factor 0.9 left and right.
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 fluidized-bed 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.
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 in reaction 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: 1 condition, raw material contacts with the cobalt-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is hydro carbons more than C5; Cobalt-based fluid catalyst used is to be selected from least one or itself and the ZrO comprising in Si or Al oxide compound
2mixture be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Co
100A
aB
bO
x
In formula, A is selected from least one in basic metal or alkaline-earth metal;
B is selected from least one in Cr, Ni, Cu or Zn;
The span of a is 0.1～10.0;
The span of b is 1.0～20.0;
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 that the value preferable range of a is 1.0～8.0, b is 2.0～18.0, and carrier consumption preferable range is 40～60% of catalyst weight by weight percentage.
The manufacture method of the catalyzer using 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 in 350～700 ℃ of roastings roasting in 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:
Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or rose vitriol for cobalt 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.
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; In addition owing to introducing Cr, Ni, Cu, Zn as catalyst adjuvant in catalyzer, promoted the dispersion of catalyst activity component at catalyst surface, thereby be conducive to improve the activity of catalyzer, solved when using fluidized-bed, the problem that heavy hydrocarbon selectivity is low, is used method of the present invention, 200～600 ℃ of temperature of reaction, reaction pressure 0.1～5.0MPa, catalyst loading 100～8000 hours
-1, proportioning raw materials (mole) H
2/ CO=0.1～5.0: carry out Fischer-Tropsch synthesis under 1 condition, CO transformation efficiency can reach 91%, and in reaction product, the selectivity of C5 and above heavy hydrocarbon can reach 73%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
After 5.23 grams of potassium hydroxide add 15 grams, water heating, dissolve, obtain material (A); 449.4 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs and 27.2 grams of nickelous nitrates are dissolved in 500 grams of 60～90 ℃ of hot water, obtain material (B).
The silicon sol that is 40% with 312.5 gram weight concentration by material (A) mixes, under agitation add material (B), 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 1700 millimeters (
millimeter) in rotary roasting furnace, in 500 ℃ of roastings 2.0 hours, make and consist of:
50％Co
100K
5.0Ni
6.0O
x+50％SiO
2。
Prepared catalyzer carries out the experimental result of Fischer-Tropsch synthesis and lists in table 1.
[embodiment 2～8]
Adopt method preparation substantially the same manner as Example 1 to have the different catalyzer that form, gained catalyzer numbering and composition are respectively:
Embodiment 1 50%Co
100k
5.0ni
6.0o
x+ 50%SiO
2.
Embodiment 2 40%Co
100na
2.0cs
2.0cr
15.0o
x+ 60%Al
2o
3
Embodiment 3 60%Co
100k
1.0mg
5.0cr
5.5ni
5.5o
x+ 40% (90%SiO
2+ 10%ZrO
2)
Embodiment 4 50%Co
100ca
1.0cr
4.0ni
2.0o
x+ 50% (80%SiO
2+ 20%Al
2o
3)
Embodiment 5 50%Co
100mg
1.5ca
2.5ni
18.0o
x+ 50% (95%Al
2o
3+ 5%ZrO
2)
Embodiment 6 55%Co
100na
3.0ca
7.0cu
8.0zn
8.0o
x+ 45% (85%Al
2o
3+ 15%ZrO
2)
Embodiment 7 50%Co
100li
5.5cr
2.0cu
6.0zn
5.0o
x+ 50% (40%SiO
2+ 40%Al
2o
3+ 20%ZrO
2)
Embodiment 8 50%Co
100cs
3.0cr
3.0ni
2.0cu
2.0zn
3.0o
x+ 50% (40%SiO
2+ 60%ZrO
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:
Comparative example 140%Co
100ni
16.0o
x+ 60%SiO
2
Comparative example 250%Co
100k
4.0o
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
| Catalyzer numbering | CO transformation efficiency % | CH 4Selectivity wt% | C 2～C 4Selectivity wt% | C 5～C 18Selectivity wt% | C 19 +Selectivity wt% | Oxygen-bearing organic matter overall selectivity wt% |
| Embodiment 1 | 89.5 | 8.3 | 18.8 | 54.9 | 17.5 | 0.5 |
| Embodiment 2 | 88.6 | 7.4 | 19.2 | 53.6 | 19.2 | 0.6 |
| Embodiment 3 | 91.1 | 9.6 | 18.5 | 54.4 | 16.8 | 0.4 |
| Embodiment 4 | 90.3 | 9 | 18.9 | 53.3 | 18.2 | 0.6 |
| Embodiment 5 | 90.8 | 9.2 | 19.4 | 52.8 | 18.1 | 0.5 |
| Embodiment 6 | 90.6 | 8.8 | 20.9 | 52.2 | 18.1 | 0.6 |
| Embodiment 7 | 89.4 | 8.0 | 19.6 | 52.4 | 19.5 | 0.5 |
| Embodiment 8 | 89.0 | 7.7 | 19.2 | 55.5 | 17.1 | 0.5 |
| Comparative example 1 | 75.7 | 18.9 | 20.7 | 46.3 | 13.6 | 0.5 |
| Comparative example 2 | 76.2 | 20.5 | 20.1 | 44.2 | 14.7 | 0.5 |
[embodiment 9]
Each step and the condition Preparation and evaluation catalyzer of pressing embodiment 3, just change appreciation condition, and its appraisal result is listed in table 2.
The evaluation result of catalyzer under table 2 different evaluation condition
| Appreciation condition | CO transformation efficiency % | CH 4Selectivity wt% | C 2～C 4Selectivity wt% | C 5～C 18Selectivity wt% | C 19 +Selectivity wt% | Oxygen-bearing organic matter overall selectivity wt% |
| 220℃ | 86.3 | 7.5 | 17.2 | 55.7 | 19.2 | 0.4 |
| 400℃ | 94.7 | 12.3 | 21.5 | 51.9 | 13.6 | 0.8 |
| 1.0MPa | 87.1 | 11.5 | 19.3 | 53.2 | 15.4 | 0.6 |
| 5.0MPa | 93.3 | 9.0 | 17.7 | 54.8 | 18.0 | 0.5 |
| 1000 hours -1 | 92.9 | 8.6 | 19.6 | 55.7 | 15.5 | 0.6 |
| 5000 hours -1 | 89.6 | 14.4 | 20.8 | 49.4 | 14.8 | 0.6 |
| H 2/CO＝1/1 | 88.5 | 8.2 | 20.2 | 56.3 | 14.9 | 0.4 |
| H 2/CO＝4/1 | 95.2 | 13.1 | 19.8 | 51.4 | 15.1 | 0.6 |
Claims (4)
1. a method for Fischer-Tropsch synthesis of heavy hydrocarbon, take synthetic gas as raw material, in reaction 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: 1 condition, raw material contacts with the cobalt-based fluid catalyst in fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is hydro carbons more than C5; Cobalt-based fluid catalyst used is to be selected from least one or itself and the ZrO comprising in Si or Al oxide compound
2mixture be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Co
100A
aB
bO
x
In formula, A is selected from least one in basic metal or alkaline-earth metal;
B is selected from least one in Cr, Ni or Zn;
The span of a is 0.1～10.0;
The span of b is 1.0～20.0;
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 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 2.0～18.0.
4. 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911693B (en) * | 2011-08-01 | 2015-04-01 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method by employing mixed catalyst |
| 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 |
| CN103589447B (en) * | 2013-11-01 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of Fischer-Tropsch synthesis method |
| CN103623828B (en) * | 2013-11-01 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of synthesizing liquid hydrocarbon cobalt-base catalyst and its preparation method and application |
| CN106540674B (en) * | 2016-10-26 | 2019-04-16 | 中科合成油技术有限公司 | A kind of metal-doped zirconia catalyst and preparation method thereof with catalyzing and synthesizing the application in gas catalyzed conversion |
Citations (3)
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|---|---|---|---|---|
| US4122110A (en) * | 1976-10-29 | 1978-10-24 | Institut Francais Du Petrole | Process for manufacturing alcohols, particularly linear saturated primary alcohols, from synthesis gas |
| CN101318133A (en) * | 2007-06-06 | 2008-12-10 | 中国科学院大连化学物理研究所 | Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof |
| CN101391219A (en) * | 2008-11-10 | 2009-03-25 | 上海兖矿能源科技研发有限公司 | FT synthesis sintered iron catalyst and preparation method and use thereof |
-
2009
- 2009-10-13 CN CN200910201618.3A patent/CN102041020B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4122110A (en) * | 1976-10-29 | 1978-10-24 | Institut Francais Du Petrole | Process for manufacturing alcohols, particularly linear saturated primary alcohols, from synthesis gas |
| CN101318133A (en) * | 2007-06-06 | 2008-12-10 | 中国科学院大连化学物理研究所 | Lamella catalyst for preparing petroleum naphtha and diesel oil, preparation method and application thereof |
| CN101391219A (en) * | 2008-11-10 | 2009-03-25 | 上海兖矿能源科技研发有限公司 | FT synthesis sintered iron catalyst and preparation method and use thereof |
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