CN100378194C - Method of coproducing oil products and electric energy using synthetic gas as raw material - Google Patents
Method of coproducing oil products and electric energy using synthetic gas as raw material Download PDFInfo
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- CN100378194C CN100378194C CNB2005101118393A CN200510111839A CN100378194C CN 100378194 C CN100378194 C CN 100378194C CN B2005101118393 A CNB2005101118393 A CN B2005101118393A CN 200510111839 A CN200510111839 A CN 200510111839A CN 100378194 C CN100378194 C CN 100378194C
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Abstract
The present invention relates to a method for simultaneously producing oil products and electric energy by using synthetic gas as the raw material. The method comprises the following steps: using Fischer-Tropsch synthesis reaction to obtain liquid hydrocarbon products, organic oxygen-containing compounds and unreacted tail gas; recovering hydrogen gas from part of the tail gas to make the liquid hydrocarbon products undergo the processes of hydrogenation, quality improvement and fractionation to obtain finished product oil; feeding the other part of the tail gas in which the hydrogen gas is not recovered and the tail gas in which the hydrogen gas is recovered into a fuel gas and vapor combined circulating electricity generator set to generate electricity; feeding at least one part of by-product vapor obtained by the Fischer-Tropsch synthesis reaction into a medium-voltage or low-voltage electricity generator set to generate electricity; collecting recovered organic oxygen-containing compounds containing no acid and using the organic oxygen-containing compounds as storage fuel for electricity generation or fuel for other processes or further processing the organic oxygen-containing compounds into high purity chemical products.
Description
Technical field
The present invention relates to a kind of is the method for raw material coproducing oil product and electric energy with the synthetic gas.
Background technology
Preparing synthetic gas with carbon raw material, to carry out Fischer-Tropsch synthetic, and coproducing oil product and electric energy are the important development directions of 21st century clean energy, in disclosed patent and document report are arranged more.
The synthetic coproduction oil of the general Fischer-Tropsch cogeneration system of recognizing according to disclosed patent and document mainly comprises following two steps:
(1) oil product is synthetic.
Synthetic gas is with H
2With CO be main mixed gas, Fischer-Tropsch synthesis can take place on fischer-tropsch synthetic catalyst.Depend on a lot of conditions by synthetic product kind and the quantity that obtains of Fischer-Tropsch, as reactor types, processing condition, catalyst mode etc.Commercialized running at present mainly contain four kinds of reactor types: tubular fixed-bed, circulating fluid bed reactor, fixed fluidized-bed reactor and slurry attitude bubbling bed reactor.These reactors may operate in high temperature and low temperature Fischer-Tropsch building-up process.Two kinds of fischer-tropsch synthetic catalysts are generally arranged: cobalt-base catalyst and ferrum-based catalyst.The product of fischer-tropsch reactor is generally by water vapour, carbonic acid gas, nitrogen, unreacted synthesis gas (H
2And CO), carburet hydrogen (C1-C5), oxygenatedchemicalss such as liquid hydrocarbon (C5+) and alcohol aldehyde keto ester are formed.General most of water vapour, liquid hydrocarbon product withdrawn and oxygenatedchemicals are condensed and separate, and final reacting product generally can be divided into the several streams thighs of tail gas, liquid hydrocarbon and reaction water.Liquid hydrocarbon is processed in derived product upgrading workshop section obtains processed oil, and reaction water is delivered to the processing of water treatment workshop section.Fischer-Tropsch process exhaust is by water vapor, CO
2, CH
4, N
2And unreacted synthesis gas (H
2+ CO), the steam hydrocarbon product forms.This tail gas can have part to loop back gasification unit, perhaps loops back Fischer-Tropsch synthesis device inlet, and burning perhaps acts as a fuel.
(2) integrated gasification combined cycle plants (IGCC) generating.
So-called combined cycle is exactly in the Rankine cycle of the steam turbine of middle cold zone work and stacked at the Bradenton round-robin of the internal combustion turbine of high-temperature zone work, form a supply system circulation, because it has eventually warm (30～40 ℃) very low after very high combustion gas initial temperature (1200 ℃～1500 ℃) and the steam work done, realized the cascade utilization of heat energy, made total cycle efficiency very high.The IGCC system then is that the synthetic gas that utilizes the carbonaceous material gasification to obtain carries out combined cycle generation as combustion gas.For polygenerations systeme, to remove outside the part that is used for synthetic oil product or chemical, synthetic gas is mainly as fuel combustion, the body turbine system of degassing electrogenesis.The turbine off-gas of heat is by the heat recovery system by-product high-pressure steam, and this high pressure steam can expand and come drive-motor to produce extra electric power by steam turbine.
Some following patents have related to existing main associating Oil Production/IGCC power plant operative technique substantially.
United States Patent (USP) 20050150820 provides a kind of gasification, hydrocarbon is synthetic and the mutually integrated process of refining of petroleum, and this method adopts membrane separation apparatus that a part of synthetic gas is divided into poor hydrogen and hydrogen-rich stream thigh, and the hydrogen-rich stream thigh mixes with synthetic gas regulates H
2/ CO ratio goes Fischer-Tropsch synthetic, goes general facilities unit byproduct steam and generating as second strand of poor hydrogen stream thigh and aforementioned poor hydrogen stream thigh after another part hydrogen-rich stream stock-traders' know-how PSA dehydrogenation.
United States Patent (USP) 20030083390 provides a kind of waste gas utilization technology, and this technology principal feature is the synthetic gas that gasification obtains to be carried out the synthetic back of Fischer-Tropsch tail gas circulated, and tail gas removes CO
2And go to generate electricity.
United States Patent (USP) 6,711,903 provide a kind of method of generating, and this method is applicable to that existing power plant transforms, and generates electricity by the part that synthetic gas Fischer-Tropsch synthetic tail gas acts as a fuel.
United States Patent (USP) 5,865,023 provides a kind of process from synthetic gas coproduction electric power and one or more chemical productss or liquid fuel, provide fuel to gas turbine by unreacted tail gas, its characteristic is the mode of raising the efficiency of its proposition, and unreacted synthesis gas heating humidification removes gas turbine again.
United States Patent (USP) 5,543,437 disclose a kind of method for preparing fischer-tropsch product and generating from coal based synthetic gas.Variation as the fuel used to generate electricity demand changes product yield according to synthetic gas.
United States Patent (USP) 4,549,396 provide a process of generating electricity with coal, generate electricity with the burning synthetic gas by coal gas being turned to synthetic gas, its characteristic is to use air to gasify, and synthetic gas is converted into liquid hydrocarbon mixture and the following gas of C4, and the following gas of C4 is used for combustion power generation, and liquid hydrocarbon mixture is used for the peak value generating.
United States Patent (USP) 4,092,825 provide a process of being generated electricity by solid carbonaceous substance, obtain synthetic gas by gasification, part synthetic gas generates mixture under catalyst action, oxygenatedchemicals hydrogenation wherein is converted to hydro carbons, and the above hydrocarbon of the C3 of acquisition and another part synthetic gas are used for generating.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of more economical and be the method for raw material coproducing oil product and electric energy flexibly with the synthetic gas in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of is that the method for raw material coproducing oil product and electric energy may further comprise the steps with the synthetic gas:
(1) Fischer-Tropsch synthesis takes place in synthetic gas in one or more levels tandem reactor, the reaction water that obtains liquid hydro-carbon products and tail gas and contain organic oxygenatedchemicals;
(2) a part of tail gas is directly sent to gas-steam combined circulating generation unit generating, and some tail gas is sent to the generating of gas-steam combined circulating generation unit again or used as the fuel of other process after recover hydrogen;
(3) during sending to, Fischer-Tropsch synthesis liberated heat byproduct steam, a part press or the generating of low-pressure steam unit;
(4) reaction water that contains organic oxygenatedchemicals is handled, be separated into the stream thigh and the acid-bearing wastewater that contain fusel, aldehyde, ketone, the stream thigh that contains fusel, aldehyde, ketone can be used as the deposit fuel of combined cycle generation, or, perhaps further be processed as chemical such as the higher alcohol of purity, aldehyde, ketone as the fuel of other process;
(5) the hydrogen hydrogenation upgrading of Fischer-Tropsch synthetic fluid hydrocarbon product by obtaining previously is multiple oil product through one or more knockout tower fractionation.
Described liquid hydro-carbon products depends on selected Fischer-Tropsch building-up process, and this process can be the high temperature fischer-tropsch building-up process, and the Fischer-Tropsch synthesis temperature is 300-380 ℃; Also can be the low temperature fischer-tropsch process, the Fischer-Tropsch synthesis temperature be 200-250 ℃.
When described Fischer-Tropsch synthesis device was single-stage, a part of tail gas looped back reactor inlet, and all the other are by described (2) individual step process; Perhaps all tail gas are all according to described (2) individual step process.
When described Fischer-Tropsch synthesis device was plural serial stage, except that the tail gas of the last stage reactor, the tail gas of each grade can or partly loop back reactor inlet, and all the other remove the next stage reactor, perhaps all remove the next stage reactor.
When described Fischer-Tropsch synthesis device was plural serial stage, the tail gas of the last stage reactor or part looped back reactor inlet, and all the other are by described (2) individual step process, perhaps all according to described the
(2) individual step process.
The hydrogenation upgrading of described liquid hydrocarbon mixture and fractionation can realize the maximization of certain oil product according to its hydrocarbon-fraction and demand, and some should not will be as the deposit fuel of generating or the fuel of other process as the cut of product.
Described dehydrogenated tail gas can remove carbonic acid gas and moisture wherein before dehydrogenation gas, freezing recovery lower carbon number hydrocarbons component wherein.
The lower carbon number hydrocarbons component of described freezing recovery mainly consists of the hydrocarbon component of C3 to C5, can be used as the deposit fuel of generating or other workshop section, also can mix further processing oil product of back with other liquid hydro-carbon products.
Described synthetic gas as raw material, also can some directly as the additional combined cycle generation that goes of combustion gas.
The described generating workshop section Fischer-Tropsch process exhaust of sending to can be removed collection to carbonic acid gas wherein.
The tail gas that described liquid hydro-carbon products hydrogenation upgrading process produces goes fuel gas pipe network or flare system.
The amount of the tail gas of described dehydrogenation is determined that by the amount of hydrogenation upgrading process need perhaps the hydrogen demand amount by other hydrogen users is determined.
The pressure of described middle pressure steam turbine unit is 3.5MPa-5.0MPa, the pressure of described lp steam turbine unit is 0.7MPa-2.0MPa, middle pressure or low pressure depend on that the Fischer-Tropsch building-up process still is a low temperature Fischer-Tropsch building-up process for the high temperature fischer-tropsch building-up process, press group during the high temperature fischer-tropsch building-up process adopts, low temperature Fischer-Tropsch building-up process adopts the low pressure unit.
Described other hydrogen users can be fuel cell or other combination producing workshop sections.
Described the stream thigh that contains fusel, aldehyde, ketone, unnecessary cut or lower carbon number hydrocarbons product as generating deposit raw material both can be used for satisfying the postcombustion of peak load generating, during also can be used for device and driving and the standby raw material during accidental state.
The outlet discharging flue gas of described fuel gas-steam circulating generation unit can be removed collection to carbonic acid gas wherein.
Described tail gas can some directly as the fuel gas of other process.
Described one or more levels series connection Fischer-Tropsch synthesis device, each grade is the Fischer-Tropsch synthesis device of one or more parallel connections.
Compared with prior art, the present invention has following characteristics:
(1) a kind of economy, feasible, the method for coproduction processed oil and electric energy are flexibly provided;
(2) directly do not adopt a large amount of synthetic gas to generate electricity, but mainly be used as fuel gas generation, the resource utilization height with tail gas;
(3) come respectively the energy of synthesis tail gas and synthetic byproduct steam is reclaimed to greatest extent by gas-steam combined circulating generation unit and middle pressure or low-pressure steam generating set;
(4) only a part of tail gas carries out recover hydrogen, to obtain liquid hydrocarbon product withdrawn hydrogenation upgrading or the required hydrogen source of other process; And most of Fischer-Tropsch process exhaust directly goes generating, and decarburization, facility investment freezing and dehydrogenation unit are reduced greatly;
(5) the organic liquid product of all or part all can be used as the deposit fuel of guarantee fuel or power plant's peak value generating;
(6) quantum of output of oil product and electric energy can be regulated as required, CO can also be effectively controlled
2Quantity discharged.
Description of drawings
Fig. 1 is the main-process stream block diagram of general oily thermoelectric coproduction device.
Figure 2 shows that a kind of Fischer-Tropsch synthesis workshop section and reaction water treatment workshop section of oily thermoelectric coproduction device of form, wherein Fischer-Tropsch synthesis is a single-stage.
Figure 3 shows that the tail gas recycle hydrogen workshop section of oily thermoelectric coproduction device.
Figure 4 shows that the hydrogenation of net product upgrading workshop section of oily thermoelectric coproduction device.
Figure 5 shows that the generating workshop section of oily thermoelectric coproduction device.
Fig. 6 is the Fischer-Tropsch synthesis workshop section and the reaction water treatment workshop section of the oily thermoelectric coproduction device of another form, and wherein Fischer-Tropsch synthesis is a two-stage series connection.
Figure 7 shows that the Fischer-Tropsch synthesis workshop section and the reaction water treatment workshop section of the oily thermoelectric coproduction device of another form, wherein the Fischer-Tropsch building-up process is the high temperature fischer-tropsch building-up process.
Figure 8 shows that the hydrogenation of net product upgrading workshop section of oily another form of thermoelectric coproduction device.
Figure 9 shows that oily another form of thermoelectric coproduction device generating workshop section.
Embodiment
The main-process stream block diagram of general with the synthetic gas is raw material coproducing oil product and electric energy as shown in Figure 1.Fischer-Tropsch synthesis takes place in synthetic gas 1 in the Fischer-Tropsch synthesis workshop section 2 that comprises one or more levels series connection Fischer-Tropsch synthesis device, generate liquid hydro-carbon products 17, reaction end gas 11 and reaction water 7.
Embodiment will reach the following examples in conjunction with the accompanying drawings and be further specified.
This embodiment process is to take into account the co-generation system of oil product output and generated energy.The Fischer-Tropsch synthetic technology adopts low temperature Fischer-Tropsch synthetic technology.Plant capacity is 800,000 tons of oil products of annual output, maximum generation ability 480MW, and wherein the Fischer-Tropsch synthesis device is a single-stage.
The Fischer-Tropsch synthesis workshop section of embodiment 1 and reaction water treatment workshop section are as shown in Figure 2.Fresh synthesis gas 21 temperature are 40 ℃, pressure 2.9MPaG, flow 780000Nm
3/ h, mole consists of H
2: 0.600, CO:0.390, CO
2: 0.004, Ar:0.001, CH
4: 0.001, N
2: 0.004.Synthetic gas 21 mixes with reaction cycle tail gas 22, mix back gas streams 23 and successively carry out preheating through two-stage interchanger 24 and 25, be preheating to 140 ℃ of paste state bed reactors 26 that enter two parallel connections, under the effect of low temperature fischer-tropsch catalysts, 2.8MPaG 230 ℃ Fischer-Tropsch synthesis takes place down, synthetic gas part in reactor is converted into the hydrocarbons of liquid phase and gas phase: liquid product 27 is separated in reactor, as paraffin wax product 29, output is 58.64t/h after interchanger 28 coolings; Gas-phase product 30 enters quenching column 31 cooling washings.As high temperature condensation product product 34, output is 22.86t/h to the part liquid phase discharging 32 of quenching column 31 bottoms after water cooler 33 coolings; A part of in addition liquid phase discharging 35 usefulness recycle pumps 36 circulation backs in interchanger 25 with 37 heat exchange of reactor inlet gas, outlet stream strands 38 further is cooled to 110 ℃ through interchanger 39 again and enters quenching column 31 cats head, making tower top outlet gas 40 temperature is 130 ℃.Gas streams 40 is earlier after after hot de-salted water water cooler 41 and water recirculator 42 be cooled to 40 ℃, enter high-pressure separator 43 and isolate liquid phase: oil phase hydrocarbons 44 was as cryogenic condensation produce product, output 19.25t/h; Water product 45 is for being rich in the reaction water of oxygenatedchemicals, output 119.63t/h.
The tail gas 55 that high-pressure separator 43 is separated is 747088Nm
3/ h is divided into two portions.Wherein the flow of stream thigh 57 is 467990Nm
3/ h, compressed machine 58 compression back Returning reactor inlets; Stream thigh 56 is 279098Nm
3/ h is divided into two strands: stream thigh 49,48115Nm
3/ h is used for recover hydrogen; Stream thigh 50,230983Nm
3/ h sends to gas-steam combined circulating generation unit as fuel gas generation.Above-mentioned tail gas mole consists of H
2O:0.003, H
2: 0.500, CO:0.300, CO
2: 0.140, Ar:0.004, CH
4: 0.026, C
2H
4: 0.003, C
2H
6: 0.001, C
3H
6: 0.002, C
3H
8: 0.001, C
4H
8: 0.002, C
4H
10: 0.001, C
5H
10: 0.002, C
5H
12: 0.001, C
6H
12: 0.001, C7:0.001, ethanol: 0.001, acetone: 0.001, N
2: 0.010.
The heat that Fischer-Tropsch synthesis produces is by reactor 26 inner cool tubes 51, mode with the feedwater byproduct steam is removed, by-product saturation steam 54 in gas bag 53, pressure is 1.6MPaG, about 538t/h, be divided into two portions: stream thigh 59,363t/h sends to the low-pressure steam generating set generating of generating workshop section; Stream thigh 60,138t/h sends to steam pipe system and uses for each workshop section.
The tail gas recycle hydrogen workshop section of embodiment 1 as shown in Figure 3.Tail gas stream thigh 49, enter dewatering unit 60 dehydrations, dehydration back stream strands 63 is cooled to about-40 ℃ through water cooler 61 and 62 two-stages, above component of most C3 and part oxygenatedchemicals are cooled and get off to become liquid in the tail gas, form gas-liquid mixed logistics 64, separate by gas-liquid separator 65: liquid portion 66 enters gas stripping column 67, emits as stream thigh 69 with most carbonic acid gas that nitrogen gas stream thigh 68 gas propose in the liquid, wherein CO
2Can further be collected; Its residual current thigh 70 is the lower carbon number hydrocarbons product, and 1.12t/h is arranged, as power plant's deposit fuel.Gas-liquid separator 65 top gas 72 become tail gas 73 after through interchanger 71 re-heats, enter pressure-swing absorption apparatus 74 and isolate wherein hydrogen, obtain 99.5% hydrogen stream thigh, 75 about 22868Nm
3/ h, this hydrogen stream stock is two portions, wherein stream thigh 76 is 18727Nm
3/ h is used for the hydrogenation upgrading of thick product, and stream thigh 77 is 4141Nm
3/ h is used for catalyst reduction.Isolate the tail gas 78 behind hydrogen, carbonic acid gas and the lighter hydrocarbons, be rich in carbon monoxide, methane and contain the small portion of residual lighter hydrocarbons, about 17825Nm
3/ h removes gas-steam combined circulating generation unit.This tail gas consists of H
2: 0.067, CO:0.806, Ar:0.010, CH
4: 0.069, C
2H
4: 0.007, C
2H
6: 0.001, C
3H
6: 0.005, C
3H
8: 0.001, C
4H
8: 0.003, C
4H
10: 0.001, C
5H
10: 0.002, N
2: 0.028.
The hydrogenation of net product upgrading workshop section of embodiment 1 as shown in Figure 4, the mixed stream of three kinds of liquid-phase products (cryogenic condensation thing 44, high temperature condensation product 34 and paraffin 29) that Fischer-Tropsch is produced strand 80 flows are 100.75t/h, at first mix with hydrogen stream thigh 82, after interchanger 83 preheatings, enter hydrotreating reactor 84.Wherein hydrogen stream thigh 82 is made up of a hydrotreatment recycle hydrogen stream thigh 85 and burst 81 mixing of hydrotreatment supply hydrogen stream, and the hydrogen stream thigh 76 that hydrotreatment supply hydrogen stream thigh 81 obtains from tail gas recycle.
In hydrotreating reactor 84, under the effect of hydrotreating catalyst, mainly carry out the hydrogenation saturated reaction of alkene, the hydrogenation and removing that also has impurity, isolate hot phase logistics 89 and hydrothermal solution logistics 90 mutually through high pressure hot separator 88 earlier through the outlet liquid hydrocarbon mixture after the hydrotreatment 87, hot phase logistics 89 enters cold high pressure separator 92 after water cooler 91 is cooled to 40 ℃.In cold high pressure separator 92, isolate high pressure vapor stream thigh 93, loop back hydrotreating reactor 84 inlets by recycle compressor 94 and use based on hydrogen; Isolated cold liquid phase stream thigh 95 is mixed into cold low separator 96 with the hot liquid phase stream thigh 90 of high pressure hot separator, and the gas 97 that obtains after the vacuum flashing is sent to flare system, and liquid 98 is introduced stripping tower 99.The gas phase 100 of stripping tower 99 is sent to the fuel gas pipe network, and separation column 103 fractionation are sent to after drawing 102 heating of liquid phase 101 heater vias in the bottom, cat head output naphtha stream thigh 104, and side line is extracted diesel stream thigh 105 out, and output tail oil 106 goes hydrocracking at the bottom of the tower.
The tail oil 107 of tail oil 106 after the follow-up hydrogenation cracking through after the hydrotreatment mixes with hydrogen stream thigh 108, enters hydrocracking reactor 110 after heater via 109 preheatings.Wherein hydrogen stream thigh 108 is made up of a hydrocracking recycle hydrogen stream thigh 111 and burst 86 mixing of hydrocracking supply hydrogen stream, and hydrotreatment supply hydrogen stream thigh 86 is from the hydrogen stream thigh 76 of tail gas recycle.
In hydrocracking reactor 110, what carry out mainly is the cracking and the isomerization reaction of hydro carbons, and macromolecule hydrocarbon is converted into the small molecules hydro carbons.Isolate hot phase logistics 114 and hydrothermal solution logistics 115 mutually through high pressure hot separator 113 earlier through the outlet liquid hydrocarbon mixture after the hydrocracking 112, hot phase logistics 114 enters cold high pressure separator 117 after interchanger 116 is cooled to 40 ℃.In cold high pressure separator 117, isolate high pressure vapor stream thigh 111 based on hydrogen, looping back hydrocracking reactor 110 inlets through recycle compressor 119 uses, isolated cold liquid phase stream thigh 118 enters cold low separator 120 with the hot liquid phase stream thigh 115 of high pressure hot separator, the gas 121 that obtains after the vacuum flashing is sent to flare system, liquid 122 is introduced stripping tower 123, the gas phase 124 of stripping tower 123 is sent to the fuel gas pipe network, separation column 127 is sent to after drawing 126 heating of liquid phase 125 heater vias in the bottom, fractionation in separation column 127, cat head output petroleum naphtha 128, side line is extracted diesel oil 129 out, 107 times isomery hydrocracking reactors of output tail oil, 110 inlets at the bottom of the tower.
Through symbiosis output diesel oil 78.80t/h and petroleum naphtha 20.05t/h after hydrotreatment and the isocracking.In year service hours 8000 hours, can produce 79.08 ten thousand tons of oil products per year.Hydrogenation upgrading workshop section produces tail gas 1.38t/h altogether, because pressure is lower and amount is few, as fuel gas generation but send to flare system or fuel gas system.
The hydrogenation of net product upgrading workshop section of embodiment 1 mainly is made up of gas-steam combined circulating generation unit workshop section and the low-pressure steam generating set two parts of workshop section as shown in Figure 5.
In gas-steam combined circulating generation unit workshop section, residual stream thigh 78 mixed streams thighs 130 behind Fischer-Tropsch process exhaust stream thigh 50 and tail gas recycle hydrogen and the lighter hydrocarbons are through preheater 131 preheatings, the gas that acts as a fuel enters the combustion chambers burn of the internal combustion turbine 132 of gas-steam combined Cycle Unit, and the high-temperature high-pressure fuel gas that the combustion chamber produces drives generating set 134 works done generating.High-temperature high-pressure fuel gas 135 temperature of internal combustion turbine unit outlet are 595 ℃, enter waste heat boiler 136, and by-product goes out 6MPa, and 520 ℃ high pressure steam 137 enters the steam turbine 138 of gas-steam combined Cycle Unit, drive generating set 139 works done generating.
Stream thigh that contains fusel, aldehyde, ketone that reclaims and lower carbon number hydrocarbons are as propellant combination stream thigh 148, and continuous 12 hours of every day stored, and are used for the postcombustion of gas-steam combined Cycle Unit in addition in 12 hours, to satisfy the peak load power generation needs.Under such operating method, 2 210MW gas-steam combined Cycle Unit have been selected for use.Generate electricity 12 hours every days under full load, while using gas and liquid fuel, generating 420MW; Under sub-load, generated electricity a using gas fuel, generating 360MW in other 12 hours.
Because steam 59 pressure ratings of Fischer-Tropsch synthesis device by-product are lower, have only 1.6MPaG, thus the steam turbine unit of combined cycle generation unit should not be entered, and need dispose independent lp steam turbine generating set separately.In low-pressure steam generating set workshop section, saturation steam 59 enters lp steam turbine 145 be superheated to 280 ℃ in well heater 143 after, drives generating set 146 generatings.The steam turbine generating set is configured to the unit of 2 30MW.
The Fischer-Tropsch synthesis workshop section of this embodiment and reaction water treatment workshop section are as shown in Figure 6.The pressure of fresh synthesis gas, flow and gas composition are identical with embodiment 1, and one-level virgin gas 150 is mixed with one-level recycled offgas 151, are preheating to 140 ℃ through interchanger 152 and interchanger 153 two-stage heat exchange, enter into one-level synthesis reactor 154.One-level synthesis reactor 154 is the paste state bed reactor of two parallel connections, and working pressure is 2.8MPaG, and service temperature is 230 ℃.Under the effect of low temperature fischer-tropsch synthetic catalyst, synthetic gas part in reactor is converted into the hydrocarbons of liquid phase and gas phase: liquid product is separated from reactor 154 as paraffin stream thigh 155, and flow is 58.64t/h; Gas-phase product 156 enters into one-level quenching column 157, part product is as stream thigh 158 at the bottom of quenching column 157 towers, carry through pump 159, with the heat exchange in interchanger 153 of reactor inlet gas, and in interchanger 160, further be cooled to 110 ℃ and enter cat head, make tower top outlet gas 162 be cooled to 130 ℃; Another part product stream thigh 161 is as high temperature condensation product product at the bottom of quenching column 157 towers, and output is 22.86t/h.Quenching column top exit gas 162 is cooled to 40 ℃ through supercooler 163 and 164 two-stages, enters high-pressure separator 165.In high-pressure separator 165, mixture is separated into gas-liquid two-phase: the oil reservoir in the liquid phase is a cryogenic condensation thing 166, and output is 19.25t/h; Water 167 is a reaction water in the liquid phase, and output is 119.63t/h; Gas phase is a tail gas 168, be divided into two portions, wherein stream thigh 170 is 467990Nm3/h, return one-level synthesis reactor 154 as recycled offgas process compressor 171 compression backs and after one-level virgin gas 150 is mixed, remaining part stream strands 169 enters second stage F-T synthesis reaction device as the virgin gas of second order reaction.
The second stage fischer-tropsch synthesis technique and first segment base are originally similar.Virgin gas 169 is heated to 140 ℃ through two sections preheaters 173 and 174 preheatings after mixing with recycled offgas 172, enter into secondary F-T synthesis reaction device 175, second reactor 175 is formed in parallel by two paste state bed reactors equally, working pressure is 2.8MPaG, service temperature is 240 ℃, and the paraffin of output stream thigh 176 is 11.52t/h in the reactor 175.Reactor head gas 177 enters secondary quenching column 178.Bottoms part stream thigh 179, preheater 174 and secondary quenching column cycle heat exchange device 181 cooling backs through second reactor 175 inlets are cooled to 110 ℃ as Quench liquid 182, power by pump 180 is sent into quenching column 178 cats head, and quenching column top exit gas 183 is cooled to 130 ℃; Another part stream thigh 198, output is 8.77t/h, as secondary high temperature condensation product product.Quenching column top exit gas 183 enters secondary high-pressure separator 186 and isolates liquid and gas after being cooled to 40 ℃ through two water coolers 184 and 185: the oil reservoir 187 in the liquid phase is secondary cryogenic condensation produce product, output 13.64t/h; Water layer 188 in the liquid phase is a reaction water, and output is 42.18t/h; The flow of vapor phase stream thigh 189 is 479471Nm
3/ h is divided into two portions: stream thigh 190, flow is 338812Nm
3/ h passes through back the mixing with secondary virgin gas 169 of compressor 191 compressions and returns second reactor 175; Rest part is stream thigh 192, flow 140659Nm
3/ h is divided into two portions again, and wherein stream thigh 193 is 115980Nm
3The dehydrogenation unit that enters/h reclaims light hydrocarbon component and hydrogen wherein, and stream thigh 194 is 24679Nm
3/ h directly enters combined cycle generation unit internal combustion turbine unit generation.Above-mentioned tail gas consists of H
2O:0.004, H
2: 0.280, CO:0.154, CO
2: 0.391, Ar:0.009, CH
4: 0.088, C
2H
4: 0.009, C
2H
6: 0.002, C
3H
6: 0.009, C
3H
8: 0.003, C
4H
8: 0.006, C
4H
10: 0.004, C
5H
10: 0.005, C
5H
12: 0.002, C
6H
12: 0.003, C
6H
14: 0.001, C7:0.001, ethanol: 0.001, acetone: 0.002, N
2: 0.026.
First stage reactor paraffin 155 and second stage reactor paraffin 176 mixed paraffin stream thighs 195, first stage reactor high temperature condensation product 161 and second stage reactor high temperature condensation product 198 mixed high temperature condensate flow thighs 196, first stage reactor high temperature condensation product 166 and second stage reactor high temperature condensation product 187 mixed high temperature condensate flow thighs 197 are sent to the hydrogenation upgrading workshop section oil that manufactures a finished product.
The heat that Fischer-Tropsch synthesis produces is removed in the mode of drum 199 and 202 byproduct steams by firsts and seconds reactor 154 and 175 inner cool tubes 201 and 203.The saturation steam 200 of by-product and 204 pressure are 1.6MPaG, and flow is respectively 538t/h and 179t/h, stream gang 520 total 717t/h after mixing, and be divided into two strands: wherein stream thigh 521 is 480t/h, sends to the steam turbine unit generation of combined cycle power plant; Stream thigh 522 is 237t/h, sends to steam pipe system and uses for each workshop section.
Tail gas recycle hydrogen workshop section's flow process and embodiment 1 are identical, reclaim lower carbon number hydrocarbons 5.24t/h, recover hydrogen 30829Nm
3/ h, wherein 25300Nm
3/ h is used for hydrogenation upgrading workshop section.The tail gas of isolating behind hydrogen, carbonic acid gas and the lighter hydrocarbons is 35952Nm
3/ h goes to gas-steam combined circulating generation workshop section.This tail gas consists of H
2: 0.045, CO:0.492, CO
2: 0.001, Ar:0.030, CH
4: 0.279, C
2H
4: 0.028, C
2H
6: 0.006, C
3H
6: 0.021, C
3H
8: 0.005, C
4H
8: 0.005, C
4H
10: 0.003, C
5H
10: 0.002, N
2: 0.083.
The flow process of hydrogenation of net product upgrading workshop section is also identical with embodiment 1.Paraffin, high temperature condensation product, the mixed stream plume of the thick product of cryogenic condensation thing amount that Fischer-Tropsch synthesis workshop section generates are 134.68t/h, with the hydrogen that reclaims, behind hydrotreatment and hydrocracking reaction, isolate diesel oil, naphtha fuel.Whole process is produced 105.20 tons/hour of diesel oil altogether, 26.76 tons/hour of petroleum naphthas.In year service hours 8000 hours, can produce 105.57 ten thousand tons of oil products per year.
Generating workshop section flow process is also identical with embodiment 1.Wherein the dehydrogenated tail gas mixing is back as combustion gas from tail gas after the dehydrogenation of Fischer-Tropsch synthesizing section, the installed capacity of the gas-steam combined circulating generation unit of configuration is separate unit 235MW, the electricity consumption every day underload period (22:00-6:00) is pressed 62% load operation, only use synthetic dehydrogenation of Fischer-Tropsch and the not air mixture of dehydrogenated tail gas, generating 145MW contains the stream thigh of fusel, aldehyde, ketone and lower carbon number hydrocarbons liquid fuel as deposit; The electricity consumption every day high loading period (6:00-22:00) then adopts gas and liquid fuel to mix as fuel used to generate electricity, the maximum 235MW that can generate electricity.Dispose 1 of low-pressure steam generating set in addition, utilize the low-pressure steam of by-product to generate electricity, installed capacity 75MW.
The Fischer-Tropsch synthesis workshop section of this embodiment and reaction water treatment workshop section are as shown in Figure 7.The temperature of fresh synthesis gas is 40 ℃, pressure 2.9MPaG, flow 833900Nm
3/ h, mole consists of H
2O:0.003, H
2: 0.661, CO:0.265, CO
2: 0.042, Ar:0.018, CH
4: 0.001, N
2: 0.010.
Synthetic gas 210 mixes with reaction cycle tail gas 211, mix back stream burst 212 priorities and carry out preheating through two-stage interchanger 213 and 215, be preheating to 150 ℃ of fixed fluidized-bed reactors 216 that enter three parallel connections, 2.8MPaG is closed in effect at the high temperature fischer-tropsch catalyzer, Fischer-Tropsch synthesis takes place under 350 ℃ the operational condition, synthetic gas part in reactor is converted into the gaseous hydrocarbons mixture, enters quenching column 223 cooling washings through the outlet vapor phase stream thigh 218 after the gas solid separation.As high temperature condensation product product 225, output is 10.43t/h to the part liquid phase discharging 224 of quenching column 223 bottoms after water cooler 226 coolings; A part of in addition liquid phase discharging 219 usefulness recycle pumps 220 circulation backs in interchanger 215 with 214 heat exchange of reactor inlet gas, working off one's feeling vent one's spleen 221 further is cooled to 110 ℃ through interchanger 222 again and enters cat head, making tower top outlet gas 227 temperature is 180 ℃.Gas streams 227 is earlier after after water cooler 228 and 229 two-stages were cooled to 40 ℃, enter high-pressure separator 230 and isolate liquid phase: oil phase hydrocarbons 236 was as cryogenic condensation produce product, output 59.95t/h; Water product 237 is for being rich in the reaction water of oxygenatedchemicals, output 159.94t/h.
Reaction water 237 enters reaction water rectifying tower 239, cat head obtains to contain the stream thigh 238 of fusel, aldehyde, ketone, flow 18.50t/h, be oxygenatedchemicalss (based on alcohol) such as the alcohol that contains 30% moisture, aldehyde, ketone, reclaim wherein each kinds alcohol, aldehyde, ketone chemical and the further derived product of processing for special chemical plant as the finished product; Waste water 240 at the bottom of the tower, and flow 141.44t/h contains methyl alcohol less than 100ppm, sends to wastewater treatment.
The tail gas 231 that high-pressure separator 230 is separated is 1049918Nm
3/ h is divided into two portions.Wherein the flow of stream thigh 232 is 780000Nm
3/ h, compressed machine 241 compression back Returning reactor inlets; Stream thigh 233 is 269918Nm
3/ h is divided into two strands: stream thigh 234,67538Nm
3/ h is used for recover hydrogen; Stream thigh 235,202380Nm
3/ h sends to gas-steam combined circulating generation unit as fuel gas generation.Above-mentioned tail gas mole consists of H
2O:0.004, H
2: 0.538, CO:0.023, CO
2: 0.170, Ar:0.068, CH
4: 0.063, C
2H
4: 0.02, C
2H
6: 0.007, C
3H
6: 0.028, C
3H
8: 0.005, C
4H
8: 0.016, C
4H
10: 0.002, C
5H
10: 0.011, C
6H
12: 0.004, C7:0.001, ethanol: 0.001, acetone: 0.001, N
2: 0.038.
The heat that Fischer-Tropsch synthesis produces is by reactor 216 inner cool tubes 217, mode with the feedwater byproduct steam is removed, by-product saturation steam 242 in gas bag 243, pressure is 3.8MPaG, about 392t/h, be divided into two portions: stream thigh 400,262t/h sends to the middle pressure steam generating set generating of generating workshop section; Stream thigh 401,130t/h sends to steam pipe system and uses for each workshop section.
Tail gas recycle hydrogen workshop section's flow process and the embodiment 1 of embodiment 3 are identical.Tail gas recycle hydrogen workshop section is recyclable 99.5% hydrogen 34518Nm altogether
3/ h, this hydrogen stream thigh 11902Nm3/h is used for the hydrogenation upgrading of thick product, and 22616Nm3/h is used for catalyst reduction and other workshop section in addition.Isolating tail gas behind hydrogen, carbonic acid gas and the lighter hydrocarbons enters fuel gas system and provides heat to give each workshop section.The also recyclable lower carbon number hydrocarbons product of this process 7.66t/h comes along hydrogenation upgrading workshop section with other fischer-tropsch product and produces final oil product.
The hydrogenation upgrading workshop section of embodiment 3 as shown in Figure 8.The material 250 that is merged together by synthetic high temperature condensation product, cryogenic condensation thing and the lower carbon number hydrocarbons product that produces of fischer-tropsch, at first enter a gas stripping column 353, carry out gas with 350 pairs of liquid of hot nitrogen and carry, overhead gas contains more CO2 and nitrogen, and a small amount of lower carbon number hydrocarbons, the torch system of reducing internal heat; The liquid flow thigh 352 that removes behind most CO2 mixes with circulation tail oil 251 and hydrogen, and the hydrogen source is fresh hydrogen 252 and circulating hydrogen 253.Reactions such as successively by hydrotreating reactor 255 and hydrocracking reactor 256, the process hydrogenation is saturated after preheater 254 preheatings for mixed material, cracking, isomerization obtain mixing liquid hydrocarbon product stream thigh 257.Stream strands 257 enters high pressure hot separator 258 through carry out heat exchange with hydrotreating reactor 255 inlet gass in interchanger 254 after, be separated into thermal high vapor phase stream thigh 259 and thermal high liquid phase stream thigh 260.Thermal high vapor phase stream thigh 259 is cooled to 40oC through water cooler 261, and being separated into hydrogen in cold high pressure separator 262 is the cold anticyclone vapor phase stream thigh 253 of main component, as the circulation hydrogen make-up; The isolated liquid phase stream thigh 263 of cold high pressure separator mixes with thermal high liquid phase stream thigh 260, enters one-level cold low separator 264 after the decompression.The vapor phase stream thigh 265 of one-level cold low separator 264 is cooled to 40 ℃ through water cooler 268 and isolates gas-liquid two-phase in secondary cold low separator 269, and gas phase 270 is gone fuel gas system, and liquid phase 271 is removed petroleum naphtha stabilizer tower 278.The liquid phase stream thigh 266 of one-level cold low separator 264 enters separation column 272 after interchanger 267 re-heats.
In separation column 272, tower middle and lower part output diesel oil distillate 275, output is 29.17t/h; Tower top output light constituent 274 separates liquid phase 271 and mixes with secondary cold low separator, enter petroleum naphtha stabilizer tower 278 after interchanger 277 re-heats; Cat head gas phase 273 enters fuel system; And tail oil 276 loops back the hydrotreating reactor inlet at the bottom of the tower after interchanger 279 heating.
In petroleum naphtha stabilizer tower 278, output petroleum naphtha 282 at the bottom of the tower, output 43.84t/h; From tower middle and upper part output liquefied petroleum gas (LPG) 281, output 5.61t/h, cat head emit light constituent 280 and send to fuel gas system.
The generating workshop section of embodiment 3 is made up of gas-steam combined circulating generation unit workshop section and the middle pressure steam generating set two parts of workshop section as shown in Figure 9.
In gas-steam combined circulating generation unit workshop section, Fischer-Tropsch process exhaust stream thigh 235 is through preheater 300 preheatings, the gas that acts as a fuel enters the combustion chambers burn of the internal combustion turbine 301 of gas-steam combined Cycle Unit, and the high-temperature high-pressure fuel gas that the combustion chamber produces drives generating set 302 works done generating.The high-temperature high-pressure fuel gas 303 of internal combustion turbine unit outlet enters waste heat boiler 304 by-products and goes out high pressure steam 305, enters the steam turbine 306 of gas-steam combined Cycle Unit, drives generating set 307 works done generating.Generating set is configured to the combined cycle generation unit of two 220MW.
In middle pressure steam generating set workshop section, the middle pressure saturation steam 400 of Fischer-Tropsch synthesis device by-product is superheated to 450 ℃ in well heater 308 after, enter middle pressure steam turbine 309, drive generating set 310 generatings.The steam turbine generating set is configured to the unit of 1 55MW.
Foregoing has been described the preferred embodiments of the invention; but should be understood to also have many adjustable places; as partial synthesis gas as fuel used to generate electricity gas; tail gas does not loop back reactor; lower carbon number hydrocarbons in the tail gas is not reclaimed etc.; each factor such as the technology that these concrete selections of improving one's methods and synthesis gas preparation adopt, the synthetic detailed process of Fischer-Tropsch and corresponding total system energy balance are directly related, but all should be in protection scope of the present invention.
Claims (18)
1. one kind is the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that this method may further comprise the steps:
(1) Fischer-Tropsch synthesis takes place in synthetic gas in one or more levels tandem reactor, the reaction water that obtains liquid hydro-carbon products and tail gas and contain organic oxygenatedchemicals;
(2) a part of tail gas is directly sent to gas-steam combined circulating generation unit generating, and some tail gas is sent to the generating of gas-steam combined circulating generation unit again or used as the fuel of other process after recover hydrogen;
(3) during sending to, Fischer-Tropsch synthesis liberated heat byproduct steam, a part press or the generating of low-pressure steam unit;
(4) reaction water that contains organic oxygenatedchemicals is handled, be separated into the stream thigh and the acid-bearing wastewater that contain fusel, aldehyde and ketone, the stream thigh that contains fusel, aldehyde and ketone can be used as the deposit fuel of combined cycle generation, or, perhaps further be processed as chemical such as the higher alcohol of purity, aldehyde and ketone as the fuel of other process;
(5) the hydrogen hydrogenation upgrading of Fischer-Tropsch synthetic fluid hydrocarbon product by obtaining previously is multiple oil product through one or more knockout tower fractionation.
2. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, described liquid hydro-carbon products depends on selected Fischer-Tropsch building-up process, and this process is the high temperature fischer-tropsch building-up process, and the Fischer-Tropsch synthesis temperature is 300-380 ℃; Or the low temperature fischer-tropsch process, the Fischer-Tropsch synthesis temperature is 200-250 ℃.
3. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that when described Fischer-Tropsch synthesis device was single-stage, a part of tail gas looped back reactor inlet, all the other are by described (2) individual step process; Perhaps all tail gas are all according to described (2) individual step process.
4. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, when described Fischer-Tropsch synthesis device is plural serial stage, except that the tail gas of the last stage reactor, the all or part of reactor inlet that loops back of the tail gas of each grade, all the other remove the next stage reactor; Perhaps except that the tail gas of the last stage reactor, all remove the next stage reactor.
5. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, when described Fischer-Tropsch synthesis device was plural serial stage, the tail gas of the last stage reactor or part looped back reactor inlet, and all the other are by described (2) individual step process; Perhaps the tail gas of the last stage reactor is all according to described (2) individual step process.
6. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, the hydrogenation upgrading of described liquid hydrocarbon mixture and fractionation realize the maximization of certain oil product according to its hydrocarbon-fraction and demand, and some should not will be as the deposit fuel of generating or the fuel of other process as the cut of product.
7. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that described dehydrogenated tail gas removed carbonic acid gas and moisture wherein before dehydrogenation gas, freezing recovery lower carbon number hydrocarbons component wherein.
8. according to claim 6 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, the lower carbon number hydrocarbons component of described freezing recovery, mainly consist of the hydrocarbon component of C3 to C5, as the deposit fuel of generating or other workshop section, perhaps mix further processing oil product of back with other liquid hydro-carbon products.
9. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, described synthetic gas as raw material, perhaps some is directly as the additional combined cycle generation that goes of combustion gas.
10. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that the described generating workshop section Fischer-Tropsch process exhaust of sending to is removed collection to wherein carbonic acid gas.
11. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that the tail gas that described liquid hydro-carbon products hydrogenation upgrading process produces goes fuel gas pipe network or flare system.
12. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, the amount of the tail gas after the described recover hydrogen is determined that by the amount of hydrogenation upgrading process need perhaps the hydrogen demand amount by other hydrogen users is determined.
13. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, the pressure of described middle pressure steam turbine unit is 3.5MPa-5.0MPa, the pressure of described lp steam turbine unit is 0.7MPa-2.0MPa, middle pressure or low pressure depend on that the Fischer-Tropsch building-up process still is a low temperature Fischer-Tropsch building-up process for the high temperature fischer-tropsch building-up process, press group during the high temperature fischer-tropsch building-up process adopts, low temperature Fischer-Tropsch building-up process adopts the low pressure unit.
14. according to claim 11 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that described other hydrogen users can be fuel cell or other combination producing workshop sections.
15. according to claim 1 or 5 or 7 described a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, described the stream thigh that contains fusel, aldehyde and ketone, unnecessary cut or lower carbon number hydrocarbons product as generating deposit raw material are during being used to satisfy the postcombustion of peak load generating or being used for device drive and the standby raw material during accidental state.
16. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that the outlet of described fuel gas-steam circulating generation unit discharging flue gas is removed collection to wherein carbonic acid gas.
17. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, described tail gas some directly as the fuel gas of other process.
18. according to claim 1 a kind of be the method for raw material coproducing oil product and electric energy with the synthetic gas, it is characterized in that, described one or more levels series connection Fischer-Tropsch synthesis device, each grade is the Fischer-Tropsch synthesis device of one or more parallel connections.
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| CN102730637B (en) | 2012-07-17 | 2014-12-10 | 武汉凯迪工程技术研究总院有限公司 | Comprehensive utilization process for low-carbon-emission Fischer-Tropsch synthesis tail gas |
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| US4549396A (en) * | 1979-10-01 | 1985-10-29 | Mobil Oil Corporation | Conversion of coal to electricity |
| CN1125866C (en) * | 2000-03-03 | 2003-10-29 | 石油大学(北京) | Process for synthesizing liquid hydrocarbon with natural gas and its synthesizing catalyst |
| CN1564781A (en) * | 2001-10-05 | 2005-01-12 | 国际壳牌研究有限公司 | System for power generation in a process producing hydrocarbons |
| US20050150820A1 (en) * | 2004-01-12 | 2005-07-14 | Chang-Jie Guo | Novell integration of gasification, hydrocarbon synthesis unit, and refining processes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4549396A (en) * | 1979-10-01 | 1985-10-29 | Mobil Oil Corporation | Conversion of coal to electricity |
| CN1125866C (en) * | 2000-03-03 | 2003-10-29 | 石油大学(北京) | Process for synthesizing liquid hydrocarbon with natural gas and its synthesizing catalyst |
| CN1564781A (en) * | 2001-10-05 | 2005-01-12 | 国际壳牌研究有限公司 | System for power generation in a process producing hydrocarbons |
| US20050150820A1 (en) * | 2004-01-12 | 2005-07-14 | Chang-Jie Guo | Novell integration of gasification, hydrocarbon synthesis unit, and refining processes |
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Application publication date: 20060614 Assignee: Shaanxi Weilai Energy Chemical Co., Ltd. Assignor: Shanghai Yankuang Energy Source Science and Technology Research Development Co. Contract record no.: 2012310000147 Denomination of invention: Method of coproducing oil products and electric energy using synthetic gas as raw material Granted publication date: 20080402 License type: Common License Record date: 20120813 |
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