CN1304913A - Process for synthesizing hydrocarbon from syntehtic gas - Google Patents

Process for synthesizing hydrocarbon from syntehtic gas Download PDF

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CN1304913A
CN1304913A CN 00121013 CN00121013A CN1304913A CN 1304913 A CN1304913 A CN 1304913A CN 00121013 CN00121013 CN 00121013 CN 00121013 A CN00121013 A CN 00121013A CN 1304913 A CN1304913 A CN 1304913A
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gas
hydrocarbon
synthetic
synthetic gas
preparation
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CN1167650C (en
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孙予罕
相宏伟
边定国
王秀芝
陈建刚
李永旺
钟炳
高海燕
张俊岭
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Zhongke Synthetic Oil Technology Co Ltd
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

A process for preparing hydrocarbon from synthetic gas includes gasifying the mixture of carbonanceous raw material, air or oxygen-enriched air and circulated C1-C4 hydrocarbon to obtain diluted nitrogen-containing synthetic gas, Fischer-Tropsch reaction in the presince of Co-base catalyst to obtain hydrocarbon, treating tail gas by combining transform reaction with pressure swing adsorption separation, returning hydrogen gas back to reactor, and returning C1-C4 hydrocarbon back to gas generating device.

Description

A kind of production method by the synthetic hydrocarbon of synthetic gas
The invention belongs to a kind of production method of synthetic hydrocarbon, relate in particular to a kind of by containing the production method of nitrogen dilution synthetic gas through the synthetic hydrocarbon of Fischer-Tropsch reaction.
As everyone knows, the gas mixture of carbon monoxide and hydrogen is called synthetic gas, and the reaction that is generated hydro carbons by synthetic gas under catalyst action is called F-T synthesis reaction.Exhausted day by day along with petroleum resources in recent years, the hydrocarbon liquids automotive fuel is shortage more and more, seek by other carbonaceous base resource such as coal, coke, Sweet natural gas, coal-seam gas, coke(oven)gas, etc. warp synthesize the approach that cyclostrophic turns to diesel oil, gasoline, kerosene and other petrochemical complex substitute products and be subjected to extensive attention.Some countries have obtained some new progresses in the technological process that the exploitation synthetic gas is converted into light class I liquid I fuel in the world.
At U.S.P4,579,986, U.S.P4,594,468, reach S.T.Sie in the CN1047275A patent at magazine Review in Chemical Engineering, disclose Dutch international Shell in 1998,14 (2), 109~157 articles of delivering and studied technological process and the method for preparing catalyst of company limited by natural gas via synthetic gas synthetic mesophase fraction oil (SMDS).The said firm's technology is H by on-catalytic self-heating partial oxidation technology with conversion of natural gas with purity oxygen 2/ CO is about 1.7 synthetic gas, simultaneously by the C that generates in the fischer-tropsch building-up process 1~C 4Hydrocarbon is produced H behind steam reformation 2, the synthetic gas that wherein a part of supply is produced makes synthetic gas advance the H of Fischer-Tropsch reaction device 2/ CO is about 2, and another part is used for heavy hydrocarbon hydrocracking and diesel oil, aviation kerosene and petroleum naphtha are produced in isomerization.The part high melting-point wax that generates is produced the commodity hard wax through hydrofining and postprocessing working procedures.The synthetic calandria type fixed bed reactor that adopts of this technology fischer-tropsch, catalyzer is the cobalt-base catalyst with immersion process for preparing.
At U.S.P4,833,170, U.S. Syntroleum company discloses by method and the device of gas production than heavy hydrocarbon in the CN1036556A patent.In this technology, Sweet natural gas and air have been adopted and the carbonic acid gas that loops back carries out autothermal reforming reaction and produces H 2/ CO is about 2 the dilution synthetic gas that contains nitrogen, and synthetic gas is produced heavy hydrocarbon by fixed bed or fluidized-bed F-T synthesis reaction then, and tail gas carries out catalyticcombustion with extra air, and generation contains CO 2And N 2Gas mixture, CO 2With N 2Separate pure N 2As product, CO 2A part is as product, and a part is recycled to the autothermal reforming reaction device and is used to make synthetic gas, and that this technology is used is Co/SiO 2Or Co/Al 2O 3Catalyzer, unstripped gas are once by the F-T synthesis reaction device.At U.S.P6, U.S. Syntroleum public affairs can disclose another novel process in 011,073 patent, and this technology is under the constant situation of above-mentioned gas making and synthetic hydrocarbon process, and subsequent step is with product hydrocarbon and water sepn, and water imports H 2/ O 2Separator, water are decomposed and become H 2With O 2Gas mixture, further be separated into H 2Stream and O 2Stream, O 2Import in the gas maker H 2Import in the raw material of synthetic gas gas, enter synthetic hydrocarbon reactor in the lump.At U.S.P5,733, U.S. Marathon oil product company is after the step of above-mentioned self-heating recapitalization gas making and synthesis reactor technology in 941 patents, increased a Brayton circulator, reaction end gas is heated to enter with pressurized air and water vapor and contains a burner, the Brayton circulator of a plurality of turbines and compressor, tail gas and air mixed combustion-driven turbine, and further drive air compressor, this process also comprises many heat exchangers from autothermal reformer outlet acquisition heat, is used for Sweet natural gas, synthetic gas and the tail gas that enters burner carry out preheating.
At U.S.P5,128,377, reach B.Wender in the CN1200140A patent at magazine FuelProcessing Technology, 1996,48, disclosing U.S. Exxon research engineering company in the article that 189-297 delivers is the AGC-21 technological process and the method for preparing catalyst of liquid fuel by conversion of natural gas, and the said firm's technology mainly contained for three steps: at first, Sweet natural gas, pure O2 and water vapor generate H in catalytic partial oxidation reactor 2/ CO is about 2 synthetic gas; Then, synthetic gas through Fischer-Tropsch reaction, generates the very wide hydrocarbon product based on wax of molecular weight ranges in the paste state bed reactor of the cobalt-base catalyst that the said firm's exploitation is housed; At last, be diesel oil, rocket engine fuel etc. with intermediates through fixed bed hydrogenation cracking and isomery upgrading.Employed cobalt-base catalyst carrier is TiO 2, contain a spot of Re or Ru.
More than the synthetic C that generates of funds-Tuo in each technological process 1~C 4Hydrocarbon does not return gas maker, and the utilization ratio of carbon is reduced; The raw material that generates synthetic gas is a Sweet natural gas, and raw material is single; Fischer-tropsch synthetic bed type is single.
Goal of the invention of the present invention provides that a kind of gas making raw material variety is many, carbon utilisation rate is high, the synthetic production method by the synthetic hydrocarbon of synthetic gas that can be applicable to multiple bed type of fischer-tropsch.
Goal of the invention of the present invention is to realize like this, gasify jointly by the lower carbon number hydrocarbons that contains carbonaceous based raw material and air or oxygen-rich air and loop back and to produce nitrogenous dilution synthetic gas, this synthetic gas under the effect of aerogel type cobalt-base catalyst through Fischer-Tropsch reaction synthin and water.After liquid hydrocarbon, heavy hydrocarbon and water sepn, tail gas makes unconverted a small amount of carbon monoxide be converted into hydrogen and carbonic acid gas through changing device, isolates H respectively through pressure-swing absorption apparatus again 2, C 1~C 4Hydrocarbon and N 2And CO 2, hydrogen is used for adjusting the carbonization of synthetic gas material hydrogen before partly turning back to the F-T synthesis reaction device, and is a part of as hydrogen product, C 1~C 4Hydrocarbon returns vapourizing furnace and produces synthetic gas.Liquid hydrocarbon is produced diesel oil, petroleum naphtha, aviation kerosene through the normal pressure distillation, and heavy hydrocarbon is through underpressure distillation production food grade hard wax, lubricant base oil and detergent raw material.
Preparation method of the present invention comprises the steps:
(1) produce the dilution synthetic gas that contains N2 by containing to gasify under carbonaceous based raw material and air or the oxygen-rich air, wherein be divided into two kinds by the difference that contains the carbonaceous based raw material:
A. be mixed in the gas maker gasification by raw coal or coke and air or oxygen-rich air, water vapor and produce the dilution synthetic gas that contains nitrogen;
B. the catalyzing part oxidation production in gas maker of Sweet natural gas, coal-seam gas or coke(oven)gas and air or oxygen-rich air contains the dilution synthetic gas of nitrogen;
(2) any dilution synthetic gas that contains nitrogen that a, b step are generated carries out the Fischer-Tropsch reaction first time under the cobalt-base catalyst effect, generates heavy hydrocarbon and water;
(3) heavy hydrocarbon, water and unreacted synthesis gas in the step (2) are carried out flash distillation, isolate heavy hydrocarbon, water, light hydrocarbon and unreacted synthetic gas, heavy hydrocarbon carries out underpressure distillation, produce lubricant base oil, food grade hard wax and wash the medicated roll raw material, light hydrocarbon and unreacted synthetic gas carry out the Fischer-Tropsch reaction second time under the cobalt-base catalyst effect;
(4) product of being produced by second time Fischer-Tropsch reaction separates the tail gas of water outlet, liquid state and solid hydrocarbons and gaseous mixture after cooling, and liquid and solid hydrocarbons is carried out air distillation and produced diesel oil, aviation kerosene, petroleum naphtha, heavy hydrocarbon;
(5) heavy hydrocarbon produced of step (4) turns back to step (3) and carries out underpressure distillation;
(6) water that flashes off of step (3) and the isolated water of step (4) is after purifying, wherein a part as and the isolated gaseous mixture of (4) step under the commercial nickel catalyst action, carry out transformationreation; Another part qualified discharge;
(7) resultant of transformationreation carries out isolating H after the transformation absorption 2, C 1~C 4Hydrocarbon, CO 2And N 2, H 2A part is returned in the synthetic gas, and a part is a product hydrogen, C 1~C 4Hydrocarbon turns back to step (1), CO 2And N 2As product.
Fig. 1 is a process flow sheet of the present invention.
In order to make the present invention be easy to allow the people understand, now specifically describe preparation method's combined process flow chart of the present invention as follows:
This process feed gas is for containing the nitrogen dilution synthesis gas, by the C that contains carbonaceous based raw material and air or oxygen-enriched air and loop back1-C 4The hydrocarbon acquisition of jointly gasifying, contain the carbonaceous based raw material comprise raw coal, coke, Natural gas, coal bed gas, oven gas etc. Because of the raw material sources difference, concrete gasification process is: (1) Raw coal or coke and air or oxygen-enriched air, water vapour are mixed in the gas maker 2 through piping 1 It is the dilution synthesis gas of 5-45% that the long-pending percentage of nitrogenous gas is produced in gasification, and nitrogenous gas amasss percentage Be preferably 5-40%, H in the synthesis gas2/ CO ratio is 1.3~2.4, and gasification temperature is 600~1300 ℃, vapor pressure 0.01-6.0MPa; (2) natural gas, coal bed gas or oven gas are raw material gas making Front need are through entering catalysis in the gas maker 2 with air or oxygen-enriched air through piping 1 behind the desulfurizing and purifying Partial oxidation is produced the dilution synthesis gas of the long-pending percentage 5-45% of nitrogenous gas, and nitrogenous gas amasss percentage Number is preferably 5-40%, H in the synthesis gas2/ CO ratio is 1.7-2.6, adopts the commercial nickel series catalysts, Reaction temperature is 600-1100 ℃, vapor pressure 0.1-2.0MPa.
The hydrogen partial mixing preparation that the synthesis gas containing nitrogen that comes out in gas maker 2 returns through pipeline 3 and pipeline 22 through conventional process such as washing, dedusting, desulfurization, deoxidation and compressions is that the long-pending percentage of nitrogenous gas is 5-45%, H2/ CO ratio is 1.3-2.6, the synthesis gas that is preferably 1.8-2.2 enters the first F-T synthesis reaction device 4, reactor 4 forms are fixed bed, slurry attitude bed or fluid bed, reaction temperature 135-280 ℃, reaction pressure is 0.7-8.0MPa, air speed is 350-10000NL/L/h, the Co/ZrO that adopts Chinese patent CN1167134 to produce2-SiO 2Or Co/ZrO2Catalyst, catalysis Agent is shaped as sphere, cylindricality, sheet, powdery etc., and fixed bed is selected sphere, cylindricality or sheet, Particle diameter is 0.5-5mm; Slurry attitude bed or fluid bed are selected sphere or powdery, and particle diameter is 0.01-2mm. The first F-T synthesis reaction device CO conversion rate control is at 60-95%. At fixed bed Containing the part diluent nitrogen in the reactor in the synthesis gas can take exothermic heat of reaction out of effectively, prevents catalyst Thereby the overheated temperature runaway of avoiding appears in bed. In slurry attitude bed or fluid bed, contain part nitrogen in the unstripped gas Gas, existing good peptizaiton stops the reunion of catalyst granules, can effectively take reaction out of again Heat release.
The reactant pipeline 5 of flowing through enters flash tank 6, and temperature is controlled between 100-200 ℃ carries out Separate, isolate heavy hydrocarbon, water, gaseous hydrocarbon and light component, heavy hydrocarbon enters decompression through pipeline 7 Distilling apparatus 8, according to the difference of vacuum distillation tower middle outlet position, it is former to produce respectively washing agent Material 9, lubricant base oil 10 and food stage hard wax 11.
Isolatedly from flash tank 6 contain the synthesis gas containing nitrogen preheating of carburet hydrogen and light component by pipe Road 12 enters the second F-T synthesis reaction device 13 and further reacts, catalyst and process conditions and First reactor is identical, makes the middle CO volumn concentration of working off one's feeling vent one's spleen of pipeline 14 less than 4%, the first Reach 92-98% with the second reactor total conversion.
The reactant that comes out from second reactor 13 pipeline 14 of flowing through enters cooling tower 15, logistics After condensation, cooling, separate water outlet, liquid state and solid hydrocarbons and gaseous mixture, from cooling tower 15 Isolated liquid state and solid hydrocarbons import in the atmospheric distillation plant 25 with pipeline 24, steam according to normal pressure Heat up in a steamer the difference of tower middle outlet position and produce respectively naphtha 27, diesel oil 28 and aviation kerosine 29, Heavy hydrocarbon at the bottom of the still is delivered in the decompression distillation 8 further refining by pipeline 26. Diesel oil 28 can be used as Diesel product also can be used as modification agent and adds in the diesel oil that PETROLEUM PROCESSING obtains, to improve diesel oil Quality. Enter only from flash tank 6 isolated water 31 with through cooling tower 15 isolated water 32 Change device 30 and purify, a part of water 34 qualified discharges after the purification, a part of water through pipeline and Admixture of gas enters converting means 17 through pipeline 16, adopts the commercial nickel series catalysts at 200-400 ℃ the carbon monoxide in the gaseous mixture is converted into hydrogen and carbon dioxide, after the cooling by pipeline 18 Be transported in the pressure-swing absorption apparatus 19.
In pressure-swing absorption apparatus 19, adopt specific surface>1300m2The carbon molecular sieve adsorbent of/g is with H2、CO 2、N 2、C 1~C 4Hydrocarbon and trace amounts of CO carry out pressure-variable adsorption and separate isolated hydrogen purity Reach 99.95%, a part is regulated synthesis gas containing nitrogen before pipeline 22 is delivered to first reactor 4 Hydrogen-carbon ratio, another part is as product hydrogen 23 output. The isolated C of pressure-variable adsorption1~C 4Hydrocarbon Enter in the gas maker 2 through pipeline 21 Returning pipes 1, to improve the utilization rate of carbon, reduce the worker The skill cost. The nitrogen 20 of the exhaust gas volumes percentage composition 96% of pressure-variable adsorption and a small amount of carbon dioxide 35, can enter atmosphere through pipeline, no environmental protection problem also can be used as product and uses.
The present invention compared with prior art has following advantage:
1. adopt the transformationreation processing tail gas that combines with PSA Technology, isolated hydrogen can be regulated the H of synthesis gas2/ CO ratio has improved the operability of installing.
2. C in the tail gas1~C 4Hydrocarbon returns gas maker, can effectively improve carbon utilisation rate, reduces the worker The skill cost.
3. contain N2Synthesis gas can effectively take reaction heat out of, make technological operation stable.
4. the aeroge type patent cobalt-base catalyst that adopts is active high, and selectively good, process is simple.
5. the synthetic catalyzer that adopts of fischer-tropsch is applicable to fixed bed, slurry attitude bed, fluidized-bed, and product structure is reasonable.
Embodiments of the invention are as follows:
Embodiment 1 one: Preparation of catalysts
Press claim 2 preparation aerogel type cobalt-base catalyst among the Chinese patent CN1167134A, obtain containing the Co/ZrO of 15% cobalt 2-SiO 2Catalyzer.
Two: generate hydrocarbon through F-T synthesis reaction
28Nm 3Sweet natural gas material and the 67Nm of/h 3The air of/h and come from the C that pipeline 21 returns 1~C 4Hydrocarbon 1.2Nm 3/ h mixes to enter catalyzing part oxidation fixed-bed reactor 2 by pipeline 1 after preheating, produces 140Nm under the nickel catalyst effect that 900 ℃, 1.0MPa, Institute of Chemical Industry, Corp., of Nanjing City are produced 3/ h contains N 2The dilution synthetic gas, N 2Volumn concentration is 39%, H 2/ CO ratio is about 1.90.
The dilution synthetic gas that from gas maker 2, comes out with come from the 1.8Nm that pipeline 22 returns 3The H of/h 2Mix, make the H in the dilution synthetic gas 2/ CO ratio is about 2.0, enters in the first F-T synthesis reaction device 4 after the compressed and preheating of synthetic gas, and above-mentioned aerogel type Co/ZrO is housed in the reactor 4 2-SiO 2Catalyzer reacts under 210 ℃ of temperature of reaction, reaction pressure 4.0MPa, air speed 2000NL/L/h condition.The reactant flow of coming out from the first F-T synthesis reaction device 4 enters flash drum 6 through pipeline 5, separates under 150 ℃ of temperature, separates obtaining the about 6Kg/h of water, the heavy hydrocarbon of about 3.01Kg/h, and the heavy hydrocarbon of 3.01Kg/h enters in the vacuum distillation apparatus 8 through pipeline 7.
That separates from flash drum 6 contains hydrocarbon gas and the light synthesis gas containing nitrogen preheating of lightweight after pipeline 12 enters the second F-T synthesis reaction device 13, be equipped with in the second F-T synthesis reaction device 13 and the identical cobalt-base catalyst of the first F-T synthesis reaction device, reaction pressure 3.8MPa, CO content from second reactor, 13 outlet tail gas is adjusted temperature of reaction, at 210 ℃ of reactions down, the CO content 2.35% in the tail gas.The reactant flow of coming out from second reactor 13 enters cooling tower 15 through pipeline 14, after 0-5 ℃ of following condensation, cooling, the about 12Kg/h of isolated water, liquid state and solid hydrocarbons and gaseous mixture, wherein liquid and solid hydrocarbons imports in the atmospheric distillation plant 25 with pipeline 24, difference according to atmospheric distillation tower 25 middle outlet positions is produced different liquid feuls respectively, and petroleum naphtha 27 is received about 1.48Kg/h<150 ℃ of boiling spreads; Aviation kerosene 29 is received about 2.50Kg/h 150-250 ℃ of boiling spread; Diesel oil 28 is received about 4.80Kg/h 250-360 ℃ of boiling spread; The about 0.7Kg/h of heavy hydrocarbon at the bottom of the still is delivered in the vacuum distillation apparatus 8 by pipeline 26.Entering cleaner 30 through pipeline 31 and cooling tower 15 isolated water through pipeline 32 from flash drum 6 isolated water purifies; a part of water 34 dischargings after the purification; part water enters changing device 17 through pipeline 33 and gaseous mixture through pipeline 16; the commercial nickel series catalysts that adopts Shanghai Chemical Research Inst to produce is converted into hydrogen and carbonic acid gas with the carbon monoxide in the gaseous mixture under 360 ℃, the cooling back is transported in the pressure-swing absorption apparatus 19 by pipeline 18.
Adopting specific surface in pressure-swing absorption apparatus 19 is 1400m 2/ g carbon molecular sieve sorbent material is with H 2, CO 2, N 2, C 1~C 4Hydrocarbon gas and trace amounts of CO carry out the transformation fractionation by adsorption, and separated hydrogen purity reaches 99.95%, wherein about 1.8Nm 3/ h hydrogen is regulated the hydrogen-carbon ratio of synthesis gas containing nitrogen before pipeline 22 is delivered to first reactor 4, remain about 4.2Nm 3/ h hydrogen 23 is exported as product hydrogen.The 1.2Nm that the transformation fractionation by adsorption goes out 3/ hC 1~C 4Hydrocarbon gas reenters in the gas maker 2 isolated N in pipeline 21 Returning pipes 1 220 and CO 2About 57Nm such as 35 gas mixtures such as grade 3/ h, wherein N 2Contain 96% approximately.Isolated N 2Gas is as product, CO 2Gas emptying.
The heavy hydrocarbon of the about 3.01Kg/h that is obtained by first synthesis reactor enters vacuum distillation apparatus 8 through pipeline 7 and pipeline 26 respectively with about 0.7Kg/h heavy hydrocarbon of the second synthesis reactor logistics at the bottom of still after the normal pressure distillation, produces detergent raw material 9 about 0.2Kg/h, lubricant base oil 10 about 2.06Kg/h and food grade hard wax 11 about 1.45Kg/h respectively according to the difference of vacuum still middle outlet position.
Embodiment 2 one: Preparation of catalysts
Press the preparation aerogel type cobalt type catalyzer of claim 4 among the Chinese patent CN1167134A, contain cobalt and be 15% Co/ZrO 2Catalyzer.
Two: generate hydrocarbon through F-T synthesis reaction
Coke adds C in air and water vapor and the circulating line 21 1-C 4Hydrocarbon 1.2Nm 3140Nm is produced in/h gas making in gas maker 2 3/ h contains N 2The dilution synthetic gas, N 2Volumn concentration is 39%, H 2/ CO ratio is about 1.90, through washing, dedusting, desulfurization, deoxidation and compression through pipeline 3 with come from the 1.8Nm that pipeline 22 returns 3The H of/h 2Mix, make the H in the dilution synthetic gas 2/ CO ratio is about 2.0, and synthetic gas enters after preheating in the first F-T synthesis reaction device 4, and above-mentioned aerogel type Co/ZrO is housed in the reactor 4 2Catalyzer reacts under 210 ℃ of temperature of reaction, reaction pressure 4.0MPa, air speed 2000NL/L/h condition.The second F-T synthesis reaction device 13,210 ℃ of temperature of reaction, reaction pressure 3.8MPa, all the other are with embodiment 1.
Embodiment 3 one: Preparation of catalysts
Press the preparation SiO of claim 3 among the Chinese patent CN1167134A 2Microspheric form cobalt type catalyzer is prepared and is contained cobalt 15%Co/ZrO 2-SiO 2Catalyzer.
Two: generate hydrocarbon through F-T synthesis reaction
60Nm 3Coke(oven)gas material and the 50Nm of/h 3The air of/h and come from the C that pipeline 21 returns 1~C 4Hydrocarbon 1.3Nm 3/ h mixes to enter catalyzing part oxidation fixed-bed reactor 2 by pipeline 1 after preheating, produces 140Nm under the nickel catalyst effect that 900 ℃, 0.7MPa, Institute of Chemical Industry, Corp., of Nanjing City are produced 3/ h contains N 2The dilution synthetic gas, N 2Volumn concentration is 34%, H 2/ CO ratio is about 2.2.Synthetic gas is compressed to be entered in the first F-T synthesis reaction device 4 by pipeline 3 with preheating, and microspheric form Co/ZrO is housed in the reactor 4 2-SiO 2Catalyzer reacts under 210 ℃ of reactions, reaction pressure 3.3MPa, air speed 2000NL/L/h condition.The reactant flow of coming out from the first F-T synthesis reaction device 4 enters flash drum 6 through pipeline 5, separates under 150 ℃ of temperature, separates obtaining the about 6Kg/h of water, the heavy hydrocarbon of about 3.0Kg/h, and the heavy hydrocarbon of 3.0Kg/h enters in the vacuum distillation apparatus 8 through pipeline 7.
The synthesis gas containing nitrogen preheating that contains hydrocarbon gas and light hydrocarbon of separating from flash drum 6 is after pipeline 12 enters the second F-T synthesis reaction device 13, be equipped with in the second F-T synthesis reaction device 13 and the identical cobalt-base catalyst of the first F-T synthesis reaction device, reaction pressure 3.1MPa, CO content from second reactor, 13 outlet tail gas is adjusted temperature of reaction, at 210 ℃ of reactions down, the CO content 3.0% in the tail gas.The reactant flow of coming out from second reactor 13 enters cooling tower 15 through pipeline 14, after 0-5 ℃ of following condensation, cooling, the about 12Kg/h of isolated water, liquid state and solid hydrocarbons and gaseous mixture, wherein liquid and solid hydrocarbons imports in the atmospheric distillation plant 25 with pipeline 24, difference according to atmospheric distillation tower 25 middle outlet positions is produced different liquid feuls respectively, and petroleum naphtha 27 is received about 1.48Kg/h<150 ℃ of boiling spreads; Aviation kerosene 29 is received about 2.5Kg/h 150-250 ℃ of boiling spread; Diesel oil 28 is received about 4.8Kg/h 250-360 ℃ of boiling spread; The about 0.6Kg/h of heavy hydrocarbon at the bottom of the still is delivered in the vacuum distillation apparatus 8 by pipeline 26.Entering cleaner 30 through pipeline 31 and cooling tower 15 isolated water through pipeline 32 from flash drum 6 isolated water purifies; a part of water 34 dischargings after the purification; part water enters changing device 17 through pipeline 33 and gaseous mixture through pipeline 16; the commercial nickel series catalysts that adopts Shanghai Chemical Research Inst to produce is converted into hydrogen and carbonic acid gas with the carbon monoxide in the gaseous mixture under 360 ℃, the cooling back is transported in the pressure-swing absorption apparatus 19 by pipeline 18.
Adopting specific surface in pressure-swing absorption apparatus 19 is 1450m 2/ g carbon molecular sieve sorbent material is with H 2, CO 2, N 2, C 1~C 4Hydrocarbon gas and trace amounts of CO carry out the transformation fractionation by adsorption, and separated hydrogen purity reaches 99.95%, and hydrogen 23 flows are about 7Nm 3/ h all exports with product.The transformation fractionation by adsorption goes out about 1.3Nm 3The C of/h 1~C 4Hydrocarbon gas reenters in the gas maker 2 isolated N in pipeline 21 Returning pipes 1 220 and CO 2About 60Nm such as 35 gas mixtures such as grade 3/ h, wherein N 2Contain 96% approximately.Isolated N 2Gas is as product, CO 2Gas emptying.
The heavy hydrocarbon of the about 3.0Kg/h that is obtained by first synthesis reactor enters vacuum distillation apparatus 8 through pipeline 7 and pipeline 26 respectively with about 0.6Kg/h heavy hydrocarbon of the second synthesis reactor logistics at the bottom of still after the normal pressure distillation, produces detergent raw material 9 about 0.2Kg/h, lubricant base oil 10 about 2.0Kg/h and food grade hard wax 11 about 1.40Kg/h respectively according to the difference of vacuum still middle outlet position.
Embodiment 4 one: Preparation of catalysts
Press claim 2 preparation aerogel type cobalt type catalyzer among the Chinese patent CN1167134A, obtain containing the Co/ZrO of 15% cobalt 2-SiO 2Catalyzer.
Two: generate hydrocarbon through F-T synthesis reaction
With hard coal, air, water vapor and come from the C that pipeline 21 returns 1~C 4Light hydrocarbon 48Nm 3/ h mixing enters in the gas maker 2 by pipeline 1 after preheating, produces 1500Nm 3/ h contains N 2Volumn concentration is 6%, synthetic gas, gas making pressure 0.05MPa, CO 2Content is 5%, H 2/ CO ratio is about 1.8.After dedusting washing, desulfating and deoxidation and compression by pipeline 3 with come from the 96Nm that pipeline 22 returns 3The H of/h 2Mix, make the H in the dilution synthetic gas 2/ CO ratio is about 2.0, and synthetic gas enters after preheating in the first F-T synthesis reaction device 4, and aerogel type Co/ZrO is housed in the reactor 2-SiO 2Catalyzer reacts under 210 ℃ of temperature of reaction, reaction pressure 2.5MPa, air speed 2000NL/L/h condition.The reactant flow of coming out from the first F-T synthesis reaction device 4 enters flash drum 6 through pipeline 5, separates under 150 ℃ of temperature, and the heavy hydrocarbon of about 50Kg/h enters in the vacuum distillation apparatus 8 through pipeline 7.Separating the heavy hydrocarbon that obtains the about 90Kg/h of water enters in the vacuum distillation apparatus 8 through pipeline 7.
The synthesis gas containing nitrogen preheating that contains hydrocarbon gas and light hydrocarbon of separating from flash drum 6 is after pipeline 12 enters the second F-T synthesis reaction device 13, be equipped with in the second F-T synthesis reaction device 13 and the identical cobalt-base catalyst of the first F-T synthesis reaction device, reaction pressure 2.4MPa, CO content from second reactor, 13 outlet tail gas is adjusted temperature of reaction, 215 ℃ of reactions down, the CO content in the tail gas is less than 4%.The reactant flow of coming out from second reactor 13 enters cooling tower 15 through pipeline 14, after 0-5 ℃ of following condensation, cooling, the about 175Kg/h of isolated water, liquid state and solid hydrocarbons and gaseous mixture, wherein liquid and solid hydrocarbons imports in the atmospheric distillation plant 25 with pipeline 24, difference according to atmospheric distillation tower 25 middle outlet positions is produced different liquid feuls respectively, and petroleum naphtha 27 is received about 24.5Kg/h<150 ℃ of boiling spreads; Aviation kerosene 29 is received about 41.5Kg/h 150-250 ℃ of boiling spread; Diesel oil 28 is received about 80Kg/h 250-360 ℃ of boiling spread; The about 11.5Kg/h of heavy hydrocarbon at the bottom of the still is delivered in the vacuum distillation apparatus 8 by pipeline 26.Entering cleaner 30 through pipeline 31 and cooling tower 15 isolated water through pipeline 32 from flash drum 6 isolated water purifies; a part of water 34 dischargings after the purification; part water enters changing device 17 through pipeline 33 and gaseous mixture through pipeline 16; the commercial nickel series catalysts that adopts Shanghai Chemical Research Inst to produce is converted into hydrogen and carbonic acid gas with the carbon monoxide in the gaseous mixture under 360 ℃, the cooling back is transported in the pressure-swing absorption apparatus 19 by pipeline 18.
Adopting specific surface in pressure-swing absorption apparatus 19 is 1500m 2/ g carbon molecular sieve sorbent material is with H 2, CO 2, N 2, C 1~C 4Hydrocarbon gas and trace amounts of CO carry out the transformation fractionation by adsorption, and separated hydrogen purity reaches 99.95%, and flow is about 96Nm 3/ h all before pipeline 22 is delivered to first reactor 4, regulates the hydrogen-carbon ratio of synthesis gas containing nitrogen.The C that the transformation fractionation by adsorption goes out 1~C 4Hydrocarbon gas 48Nm 3/ h reenters in the gas maker 2 isolated N in pipeline 21 Returning pipes 1 220 and CO 2About 185Nm such as 35 gas mixtures such as grade 3/ h, wherein N 2Contain 96% approximately.Isolated N 2Gas is as product, CO 2Gas emptying.
The heavy hydrocarbon of the about 50Kg/h that is obtained by first synthesis reactor enters vacuum distillation apparatus 8 through pipeline 7 and pipeline 26 respectively with about 11.5Kg/h heavy hydrocarbon of the second synthesis reactor logistics at the bottom of still after the normal pressure distillation, produces detergent raw material 9 about 3.5Kg/h, lubricant base oil 10 about 35.0Kg/h and food grade hard wax 11 about 23Kg/h respectively according to the difference of vacuum still middle outlet position.

Claims (12)

1. the preparation method by the synthetic hydrocarbon of synthetic gas is characterized in that comprising the steps:
(1) gasification production contains N under carbonaceous based raw material and air or the oxygen-rich air by containing 2The dilution synthetic gas, wherein be divided into two kinds by the difference that contains the carbonaceous based raw material:
A. be mixed in the gas maker gasification by raw coal or coke and air or oxygen-rich air, water vapor and produce the dilution synthetic gas that contains nitrogen;
B. the catalyzing part oxidation production in gas maker of Sweet natural gas, coal-seam gas or coke(oven)gas and air or oxygen-rich air contains the dilution synthetic gas of nitrogen;
(2) any dilution synthetic gas that contains nitrogen that a, b step are generated carries out the Fischer-Tropsch reaction first time under the cobalt-base catalyst effect, generates heavy hydrocarbon and water;
(3) heavy hydrocarbon, water and unreacted synthesis gas in the step (2) are carried out flash distillation, isolate heavy hydrocarbon, water, light hydrocarbon and unreacted synthetic gas, heavy hydrocarbon carries out underpressure distillation, produce lubricant base oil, food grade hard wax and wash the medicated roll raw material, light hydrocarbon and unreacted synthetic gas carry out the Fischer-Tropsch reaction second time under the cobalt-base catalyst effect;
(4) product of being produced by second time Fischer-Tropsch reaction separates the tail gas of water outlet, liquid state and solid hydrocarbons and gaseous mixture after cooling, and liquid and solid hydrocarbons is carried out air distillation and produced diesel oil, aviation kerosene, petroleum naphtha, heavy hydrocarbon;
(5) heavy hydrocarbon produced of step (4) turns back to step (3) and carries out underpressure distillation;
(6) water that flashes off of step (3) and the isolated water of step (4) is after purifying, wherein a part as and the isolated gaseous mixture of (4) step under the commercial nickel catalyst action, carry out transformationreation; Another part qualified discharge;
(7) resultant of transformationreation carries out isolating H after the transformation absorption 2, C 1~C 4Hydrocarbon, CO 2And N 2, H 2A part is returned in the synthetic gas, and a part is a product hydrogen, C 1~C 4Hydrocarbon turns back to step (1), CO 2And N 2As product.
2. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1, it is characterized in that described processing condition by raw coal or coke production synthetic gas are: gasification temperature is 600~1300 ℃, vapor pressure 0.01-6.0MPa.
3. a kind of preparation method according to claim 1 by the synthetic hydrocarbon of synthetic gas, it is characterized in that described processing condition by Sweet natural gas, coal-seam gas or coke(oven)gas generation synthetic gas are: adopt the commercial nickel series catalysts, temperature of reaction is 600-1100 ℃, vapor pressure 0.1-2.0MPa.
4. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that described to contain nitrogen dilution synthetic gas nitrogen content volume percent be 5-45%.
5. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that described reaction conditions at first F-T synthesis reaction and second F-T synthesis reaction is: H 2/ CO ratio is 1.3-2.6, and temperature of reaction 135-280 ℃, reaction pressure is 0.7-8.0MPa, and air speed is 350-10000NL/L/ hour; The cobalt type catalyzer that adopts CN1167134 to produce.
6. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that CO content is lower than the CO overall budget transformation efficiency of 4%, two F-T synthesis reaction device greater than 92% in the described control second Fischer-Tropsch reaction device outlet tail gas.
7. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1, it is characterized in that the separation condition of described flash drum is: temperature is controlled between 100-200 ℃.
8. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that the processing condition of described transformationreation are: adopt the commercial nickel series catalysts at 200-400 ℃ the carbon monoxide in the tail gas to be converted into hydrogen and carbonic acid gas.
9. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that the sorbent material of described transformation absorption is a carbon molecular sieve.
10. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that described to contain nitrogen dilution synthetic gas nitrogen content volume percent be 5-40%.
11. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 1 is characterized in that described H 2/ CO is than being 1.8-2.2.
12. a kind of preparation method by the synthetic hydrocarbon of synthetic gas according to claim 9, the sorbent material specific surface area that it is characterized in that described transformation absorption is greater than 1300m 2The carbon molecular sieve of/g.
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