CN102041020A - Fluidized bed Tropsch synthesis method for heavy hydrocarbons - Google Patents
Fluidized bed Tropsch synthesis method for heavy hydrocarbons Download PDFInfo
- Publication number
- CN102041020A CN102041020A CN2009102016183A CN200910201618A CN102041020A CN 102041020 A CN102041020 A CN 102041020A CN 2009102016183 A CN2009102016183 A CN 2009102016183A CN 200910201618 A CN200910201618 A CN 200910201618A CN 102041020 A CN102041020 A CN 102041020A
- Authority
- CN
- China
- Prior art keywords
- reaction
- tropsch synthesis
- fluidized bed
- catalyst
- heavy hydrocarbon
- 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.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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
Is that nineteen twenty-three is by Germany scientist Frans Fischer and Hans Tropsch invention with synthetic gas through the method that catalyst action is converted into liquid hydrocarbon, it is synthetic to be called for short F-T, be that the heterogeneous catalysis hydrogenation takes place on metal catalyst CO, generate process based on the mixture of straight-chain paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and has realized industrialization in 1936, after World War II because of closing with the petroleum industry competition economically; South Africa has the abundant in coal resource, but the petroleum resources plaque is weary, and be subjected to the restriction of international community's economy and political sanction for a long time, force its development coal-to-oil industry technology, and built up first coal-based F-T synthetic oil factory (Sasol-1) that throughput is ten thousand tons of product/years of 25-40 in 1955.
Twice world oil crisis of 1973 and 1979 causes world's crude oil price to fall and swings fluctuating, big rise and big fall, and based on the consideration of strategic tachnical storage, the 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 build up in succession again and gone into operation of South Africa Sasol company.But plummeting of world's oil price in 1986 postponed the F-T synthetic technology in other national heavy industrialization process.
Twentieth century is since the nineties, and petroleum resources are shortage and poor qualityization day by day, and coal and Sweet natural gas proven reserve but constantly increase simultaneously, and the GTL technology causes extensive concern once more.Through the development of decades, Fischer-Tropsch catalyst has also obtained significant progress, and catalyzer commonly used at present is divided into two big classes on active ingredient: ferrum-based catalyst and cobalt-base catalyst.According to the difference of employing catalyzer and the difference of target product, the Fischer-Tropsch synthesis device is divided into fixed-bed reactor, fluidized-bed reactor and paste state bed reactor again.The fixed-bed reactor complex structure costs an arm and a leg, and removes the heat difficulty, and the production capacity of whole device is lower.The characteristics of slurry attitude bed are that temperature of reaction is lower, be easy to control, but transformation efficiency are lower, and the liquid-solid separation that product mostly is slurries in high-carbon hydrocarbon and the reactor is comparatively difficult.The characteristics of fluidized-bed reactor are that temperature is higher, and transformation efficiency is higher, do not have liquid-solid isolating difficulty, 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 remove the heat of emitting in the dereaction, because gas line speed is low, and wear problem is less, this makes long-term operation become possibility simultaneously.
Cobalt-base catalyst is owing to have the per pass conversion height, and the life-span is long, straight chain hydrocarbon yield height; Stable and be difficult for carbon distribution and poisoning in the reaction process, advantage such as oxygenatedchemicals is few in the product, and water gas shift reaction is insensitive; Main drawback has: cost an arm and a leg, the catalyzer warm area is narrow, and adjustability is poor.Therefore, the Co base F-T catalyzer that has prospects for commercial application at present is loading type basically, or the mixture of Co and the formation of other metal oxide.CN1764499A report be applied to fluidized-bed Fischer-Tropsch synthetic cobalt-base catalyst, this catalyzer is by preparing on the silicon-dioxide base carrier that two or more is comprised the metal precursor compound that is selected from cobalt, nickel and ruthenium and be impregnated into alkali metal containing and/or alkaline-earth metal, at pressure 1MPa, 250 ℃ of temperature of reaction, catalyst loading 2000 hours
-1, unstripped gas H
2Under the condition of/CO=2/1, the CO transformation efficiency is about 90%, methane selectively about 13%, the chainpropagation factor about 0.9.
Summary of the invention
Technical problem to be solved by this invention is in the prior art because Fischer-Tropsch synthesis is a strong exothermal reaction, and when using fixed bed, the heat difficulty is removed in reaction, and easily temperature runaway makes the easy inactivation of catalyzer; When using fluidized-bed, the problem that selectivity is low provides a kind of method of new fluidized-bed Fischer-Tropsch synthesis of heavy hydrocarbon.This method fluidized-bed reactor, it is fast to have the heat of removing, the advantage that the 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 is a raw material with the synthetic gas, is 0.5～10MPa in reaction pressure, and temperature of reaction is 200～600 ℃, and reaction velocity is 100～8000 hours
-1, H in the unstripped gas
2/ CO mol ratio is under 0.1～5.0: 1 the condition, and raw material contacts with cobalt-based fluid catalyst in the fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is the above hydro carbons of C5; Used cobalt-based fluid catalyst comprises at least a in Si or the Al oxide compound or itself and ZrO to be selected from
2Mixture be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Co
100A
aB
bO
x
A is selected from least a in basic metal or the alkaline-earth metal in the formula;
B is selected from least a among Cr, Ni, Cu or the Zn;
The span of a is 0.1～10.0;
The span of b is 1.0～20.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
The carrier consumption is 30～70% of catalyst weight by weight percentage.
In the technique scheme, the value preferable range of a is 1.0～8.0, and the value preferable range of 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 that uses in the inventive method there is no particular requirement, can be undertaken by well-established law.At first the catalyzer each component is made solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to is made catalyzer in 350～700 ℃ of roastings roasting in 0.5～5 hour at last.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyzer of the present invention is:
Cobalt component in the catalyzer is with Xiao Suangu or rose vitriol.
The most handy its nitrate of all the other components, oxyhydroxide maybe can be decomposed into the salt of oxide compound.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silicon-dioxide.If use silicon sol, its quality will meet the requirement of CN1005248C.
Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyzer of making has good size-grade distribution with centrifugal better.
The roasting of catalyzer can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyzer.The 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 be divided into two zones in a stove, also can finish simultaneously in the continous way rotary roasting furnace and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air, to generate the catalytic activity 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, when 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
-1Reduction 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
-1Unstripped gas H
2/ CO is preferably 0.5～3.0 than for than being 0.1～5.0.
Because the present invention adopts fluidized-bed process, therefore solved in the prior art because Fischer-Tropsch synthesis is a strong exothermal reaction, when using fixed bed, the heat difficulty is removed in reaction, and easy temperature runaway makes the problem of the easy inactivation of catalyzer; In addition owing in catalyzer, introduce Cr, Ni, Cu, Zn as catalyst adjuvant, promoted of the dispersion of catalyst activity component at catalyst surface, thereby help improving activity of such catalysts, solved when using fluidized-bed, the problem that the 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
2Carry out Fischer-Tropsch synthesis under the condition of/CO=0.1～5.0: 1, the CO transformation efficiency can reach 91%, C in the reaction product
5The selectivity that reaches above heavy hydrocarbon can reach 73%, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
5.23 gram potassium hydroxide adds water 15 grams and the dissolving of heating back, obtains material (A); 449.4 gram Xiao Suangus and 27.2 gram nickelous nitrates are dissolved in 60～90 ℃ of hot water of 500 grams, get material (B).
With material (A) and 312.5 gram weight concentration is that 40% silicon sol mixes, under agitation add material (B), the acidity of regulating above-mentioned slurry with ammoniacal liquor makes the pH=6.0 of mixed slurry, after fully stirring, get slurry, according to well-established law the slurry of making is carried out the framboid moulding in spray-dryer, be 89 millimeters at internal diameter at last, length be 1700 millimeters (
) 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 of forming, 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%Zr0
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 of forming, gained catalyzer numbering and composition are respectively:
Comparative example 1 40%Co
100Ni
1.60O
x+ 60%SiO
2
Comparative example 2 50%Co
100K
4.0O
x+ 50%SiO
2
Prepared catalyzer carries out Fischer-Tropsch synthesis under following reaction conditions, the result also lists in table 1.
The reductive condition of the foregoing description and comparative example is:
Reaction conditions is:
The evaluation result of table 1 embodiment catalyzer
[embodiment 9]
Press each step and condition preparation and the evaluate catalysts of embodiment 3, just change appreciation condition, its appraisal result is listed in table 2.
The evaluation result of catalyzer under the table 2 different evaluation condition
Claims (4)
1. the method for a Fischer-Tropsch synthesis of heavy hydrocarbon is a raw material with the synthetic gas, is 0.5～10MPa in reaction pressure, and temperature of reaction is 200～600 ℃, and reaction velocity is 100～8000 hours
-1, H in the unstripped gas
2/ CO mol ratio is under 0.1～5.0: 1 the condition, and raw material contacts with cobalt-based fluid catalyst in the fluidized-bed, and reaction generates heavy hydrocarbon, and wherein heavy hydrocarbon is the above hydro carbons of C5; Used cobalt-based fluid catalyst comprises at least a in Si or the Al oxide compound or itself and ZrO to be selected from
2Mixture be carrier, active ingredient contains with the following composition of atomic ratio measuring chemical formula:
Co
100A
aB
bO
x
A is selected from least a in basic metal or the alkaline-earth metal in the formula;
B is selected from least a among Cr, Ni, Cu or the Zn;
The span of a is 0.1～10.0;
The span of b is 1.0～20.0;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
The carrier consumption is 30～70% of catalyst weight by weight percentage.
2. according to the method for the described Fischer-Tropsch synthesis of heavy hydrocarbon of claim 1, the span that it is characterized in that a is 1.0～8.0.
3. according to the method for the described Fischer-Tropsch synthesis of heavy hydrocarbon of claim 1, the span that it is characterized in that b is 2.0～18.0.
4. according to the method for the described Fischer-Tropsch synthesis of heavy hydrocarbon of claim 1, it is characterized in that the carrier consumption is 40～60% of catalyst weight by weight percentage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910201618.3A CN102041020B (en) | 2009-10-13 | 2009-10-13 | Fluidized bed Tropsch synthesis method for heavy hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910201618.3A CN102041020B (en) | 2009-10-13 | 2009-10-13 | Fluidized bed Tropsch synthesis method for heavy hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102041020A true CN102041020A (en) | 2011-05-04 |
| CN102041020B CN102041020B (en) | 2014-01-22 |
Family
ID=43907570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910201618.3A Active CN102041020B (en) | 2009-10-13 | 2009-10-13 | Fluidized bed Tropsch synthesis method for heavy hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102041020B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911693A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method by employing mixed catalyst |
| CN103589447A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN103623828A (en) * | 2013-11-01 | 2014-03-12 | 中国石油化工股份有限公司 | Synthetic liquid hydrocarbon cobalt-based catalyst and preparation method and application 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 |
| CN106540674A (en) * | 2016-10-26 | 2017-03-29 | 中科合成油技术有限公司 | A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized |
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 |
-
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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911693A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method by employing mixed catalyst |
| 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 |
| CN103589447A (en) * | 2013-11-01 | 2014-02-19 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN103623828A (en) * | 2013-11-01 | 2014-03-12 | 中国石油化工股份有限公司 | Synthetic liquid hydrocarbon cobalt-based catalyst and preparation method and application thereof |
| 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 |
| CN106540674A (en) * | 2016-10-26 | 2017-03-29 | 中科合成油技术有限公司 | A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102041020B (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101993707B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbon | |
| CN102452878B (en) | Method for preparing low-carbon olefin by synthetic gas one-step technology | |
| 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 | |
| CN103664447A (en) | Method for preparing olefine from synthesis gas | |
| CN102041021B (en) | Method for synthesizing heavy hydrocarbon by fischer-tropsch | |
| CN104549343B (en) | Preparation of low carbon olefines by synthetic gas catalyst, preparation method and its usage | |
| CN105363464A (en) | Catalyst for directly preparing light hydrocarbon through synthesis gas and preparation method of catalyst | |
| CN102041020B (en) | Fluidized bed Tropsch synthesis method for heavy hydrocarbons | |
| CN105363458B (en) | Synthesize catalyst of light hydrocarbon and preparation method thereof | |
| CN105363463B (en) | Catalyst of synthesis gas light hydrocarbon and preparation method thereof | |
| CN106607053B (en) | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof | |
| CN103664436A (en) | Method for directly transforming synthesis gas into low-carbon olefin | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN102039135B (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN105435803A (en) | A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst | |
| CN109647426A (en) | The ferrum-based catalyst of the direct producing light olefins of synthesis gas | |
| CN103418393B (en) | The Catalysts and its preparation method of Fischer-Tropsch synthesis of heavy hydrocarbon | |
| CN102039133B (en) | Fischer-Tropsch synthesized Co-based fluidized bed catalyst and preparation method thereof | |
| CN103666517A (en) | Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis | |
| CN111036284A (en) | Catalyst, preparation method thereof and method for preparing low-carbon olefin from synthesis gas | |
| CN101993706A (en) | Method for tropsch synthesis of hydrocarbon containing five or more carbon atoms | |
| CN103721718A (en) | Catalyst for preparing advanced hydrocarbon by Fischer-Tropsch synthesis and preparation method of catalyst | |
| CN103521238B (en) | Micro spherical Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN103657676B (en) | Microspherical Fischer-Tropsch catalyst and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |