CN101210186A - Solvent and method for removing carbon dioxide from Fischer-Tropsch synthesis circulation gas - Google Patents

Solvent and method for removing carbon dioxide from Fischer-Tropsch synthesis circulation gas Download PDF

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CN101210186A
CN101210186A CNA2006101663036A CN200610166303A CN101210186A CN 101210186 A CN101210186 A CN 101210186A CN A2006101663036 A CNA2006101663036 A CN A2006101663036A CN 200610166303 A CN200610166303 A CN 200610166303A CN 101210186 A CN101210186 A CN 101210186A
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CN101210186B (en
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王祥云
刘蓓
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

The invention relates to a solvent and a method for removing CO2 in mixture gas of recycling gas of Fischer-Tropsch synthesis. A carbon removal solution comprises potassium carbonate, an inhibitor, an inorganic activator and an organic activator. The method comprises removing the majority of oxygen-containing organic matters and heavy hydrocarbons containing more than six carbon atoms in the recycling gas by a water washing tower and recovering the organic matters via waste water treatment; flash-evaporating the majority of H2, CO and light hydrocarbons dissolved in a rich liquid by a rich liquid flash tank, and recovering; and desorbing the solvent by using pressure swing regeneration and power saving technology. During removal of CO2 in the recycling gas of Fischer-Tropsch synthesis, the invention adopts the carbon removal process to achieve low hydrocarbon loss and good solution stability and to overcome the disadvantage of high regeneration heat consumption. The regeneration heat consumption is not larger than 344 kJ/Nm<3>CO2, which is lower than that of the conventional potassium carbonate process by over 30%.

Description

A kind of solvent of removing carbon dioxide from Fischer-Tropsch synthesis circulation gas and method
Technical field:
The invention belongs to the gas purification technique field, be specifically related to a kind ofly from the Fischer-Tropsch synthesis or F-T circulation gas that contains a large amount of hydro carbons and a small amount of oxygen-bearing organic matter, remove CO 2Method.
Background technology:
With coal or Sweet natural gas is the raw material production oil product, adopts Fischer-Tropsch synthesis process usually, in fischer-tropsch reaction, and H 2Produce water with CO going back on the ortho states catalyzer reduction dissociation process, water carries out transformationreation, CO+H with CO on ferrum-based catalyst surface particularly again 2O → CO 2+ H 2, generate a large amount of CO 2, owing to gas composition difference, catalyzer difference, operational condition difference, the degree of transformationreation has difference; In order to improve the oil product productive rate, the tail gas that goes out tower after the reaction need recycle, and at first the liquid product that goes out in the synthetic tower gas is separated, again with the CO in the tail gas 2Remove, send synthetic tower back to by recycle compressor at last.
In the middle of having come out to separate the circulation gas behind the oil product from the Fischer-Tropsch synthesis device, the content of hydro carbons accounts for 15~30%, when wherein particularly adopting ferrum-based catalyst, alkene and the carbon heavy paraffin hydrocarbon class more than 4 accounts for 20~50%, also have oxygen-bearing organic matters such as a spot of aldehyde, ketone, pure and mild acid, therefore, select decarbonization process also special requirement will be arranged, mainly contain three aspects.
The one, " the hydrocarbon loss " that compare different process reduces hydrocarbon loss, just can not adopt physical solvent when selecting decarbonization method, must select the chemical reaction decarbonization method.T.P.Shaw and P.W.Hughes are after May calendar year 2001, " Hydrocarbon Processing " magazine carried out relative merits and adaptive comparison to various decarbonization methods, with an offshore platform output CO 2The oil field gas production NGL of content 5~10% is an example, and wherein " the hydrocarbon loss relatively " salt of wormwood decarbonization process hydrocarbon loss is minimum, is 0.8%, (seeing Table 1).Bring up under 108~118 ℃ the situation in rich solution temperature at the bottom of the absorption tower, the hydrocarbon loss can be still less, and therefore, removing carbon dioxide from Fischer-Tropsch synthesis circulation gas suits to adopt the salt of wormwood decarbonization process.
The hydrocarbon loss of the various decarbonization process of table 1. relatively
Decarbonization process Hydrocarbon loss (%)
The amine method 1.2
The salt of wormwood method 0.8
Physical solvent process 100
Mixed solvent method 9.9
Membrane sepn The hydrocarbon loss can't be accepted
The 2nd, consider the stability of solution, because formaldehyde can be rapidly and organic amine activator in the heat of activation salt of wormwood method, for example the activator diethanolamine (DEA) in the Benfield decarbonizing solution reacts generation alkyl ammonia methyl alcohol (HOCH 2CH 2) 2NCH 2OH, alkyl ammonia methyl alcohol under heating or alkaline condition, with diethanolamine again condensation generate substituted methylene amine (HOCH 2CH 2) 2NCH2N (CH 2CH 2OH) 2These by products have not only consumed activator, also make solution rotten, and viscosity increases, easily foaming, and seriously corroded, influences decarburization capacity.Therefore, adopt " activated heat potassium carbonate process " must select the activator of good stability at removing carbon dioxide from Fischer-Tropsch synthesis circulation gas.
The 3rd, be at the high shortcoming of salt of wormwood decarbonization process regeneration hear rate, the various new technologies that employing is developed both at home and abroad, novel process are to reduce the regeneration hear rate.
Summary of the invention:
The objective of the invention is solvent and method, be characterized at a kind of removing carbon dioxide from Fischer-Tropsch synthesis circulation gas of top 3 propositions:
(1) composition of solvent comprises that salt of wormwood, inhibiter, activator are mineral compound and organic compound; Salt of wormwood weight concentration 10~40% (preferred 20~30%), inhibiter: Vanadium Pentoxide in FLAKES weight concentration 1~10% (preferred 2~7%), inorganic activator boric acid, metaantimmonic acid, telluric acid, selenous acid, a kind of or its mixture weight concentration 1~30% (preferred 2~20%) in the Vanadium Pentoxide in FLAKES, the organic activator Padil, hydroxyethyl diamine, diethanolamine, quadrol, Diethylenetriaminee (DETA), the dihydroxy ethyl quadrol, imidazoles, Methylimidazole, tetramethylene sulfone, N-cyclohexyl 1,3 propylene diamine, 2 amino-2 methyl isophthalic acid propyl alcohol, dimethylamino-2-propyl alcohol, 2 piperidines ethanol, a kind of or its mixture weight concentration in the 2-ethylaminoethyl alcohol is 0~20% (preferred 0~10%);
(2) adopt in the water wash column flush away circulation gas most of oxygen-bearing organic matter and the heavy hydrocarbon of carbon 6 or more and by the waste water treatment and reclamation organism in the flow process, the absorption employing activates solution of potassium carbonate as mentioned above, and the rich solution after the absorption reclaims most of H by flash distillation 2, CO and lighter hydrocarbons, the pressure that absorbs operation is that circulation gas separates back pressure, pressure is 1.0~10.0Mpa, absorbs 60~110 ℃ of service temperatures of cat head (preferred 90~120 ℃), the pressure swing regeneration technology is adopted in the desorb of solution.
(3) adopt in the water wash column flush away circulation gas most of oxygen-bearing organic matter and the heavy hydrocarbon of carbon 6 or more also by the waste water treatment and reclamation organism, washing pressure is that circulation gas separates back pressure, be generally 1.0~10.0Mpa, water temperature is controlled at 0~100 ℃ (preferred 20~80 ℃), and water/gas ratio is controlled at 1m 3Water: 100~10000Nm 3Gas (is preferably 1m 3Water: 300~3000Nm 3Gas).
(4) adopt the rich solution flash drum on stream, flash off the most of H that is dissolved in the rich solution 2, CO and lighter hydrocarbons, reclaim and use.The working pressure of rich solution flash drum can be in 0.1~1.6Mpa scope, and service temperature is 70~125 ℃ (being preferably 90~120 ℃).
(5) the pressure swing regeneration power-saving technology is adopted in the desorb of solution, utilizes the flash distillation of pressurization regeneration overhead to come out to have the CO of certain pressure 2Aspirate normal pressure regenerator column as power by " subsonic speed injector " with water vapour, form pressure reduction between two towers, the regeneration overhead of wherein pressurizeing pressure-controlling is at absolute pressure 0.15~0.35Mpa, be preferably absolute pressure 0.17~0.28Mpa, normal pressure regeneration overhead pressure-controlling is absolute pressure 0.05~0Mpa or 0~-0.05 Mpa (vacuum) (be preferably absolute pressure 0.04~-0.03Mpa vacuum), make that the solution boiling point produces 15~30 ℃ the temperature difference (being generally 20~25 ℃) at the bottom of two towers, thereby realize that the heat energy classification repeatedly utilizes, and reaches energy-conservation purpose.It comprises: the solution in the normal pressure regenerator column under the suction function of injector, gas phase CO 2Dividing potential drop reduces, and the solution stripping impellent strengthens, and has saved the regeneration hear rate; Have that flash distillation discharges a large amount of water vapour in the lean solution flash drum of lean solution under pressure-fired or vacuum condition of certain temperature, pressure, the semi lean solution gas of supplying with in the normal pressure regenerator column is proposed regeneration, saved the regeneration steam consumption, the lean solution temperature after the flash distillation reduces by 15~25 ℃ of calorific losss that also reduced lean solution cooling in the lean solution water cooler; The waste heat of 130~145 ℃ of vapour of pressurization regeneration bottom steam boiling device I outlet, water mixture can also be used for heating semi lean solution once more in normal pressure regenerator column bottom steam boiling device II, improved the utilising efficiency of steam.
Adopt the present invention when removing carbon dioxide from Fischer-Tropsch synthesis circulation gas, can keep " the hydrocarbon loss is low ", " stability of solution is good ", overcome the shortcoming of " regeneration hear rate height " simultaneously, reduce more than 30% than routine activation salt of wormwood decarbonization process regeneration hear rate.
At being raw material, by the actual conditions of Fischer-Tropsch synthesis production oil product, because of synthetic gas H with coal or Sweet natural gas 2/ CO is than different, adopt catalyzer difference, isothermal tubulation Fischer-Tropsch synthesis device or paste state bed reactor difference, the composition of Fischer-Tropsch synthetic tower outlet tail gas is also different, develop that adapt, complete, " removing carbon dioxide from Fischer-Tropsch synthesis circulation gas method " that best set becomes to make up, not only the good stability of solution, activator is active high, guarantee the assimilated efficiency of decarbonizing solution, the solution absorption ability is 20~40Nm 3CO 2/ m 3Solution; Because the condition that characteristics, the service temperature of hot potassium carbonate solution self are high and set up water wash column, most of oxygen-bearing organic matter in the circulation gas and carbon are sent into the decarburization absorption tower after the heavy hydrocarbon flush away 6 or more again and made " hydrocarbon loses minimum " of circulation gas; Simultaneously, integrated " pressure swing regeneration decarburization technique " makes regeneration hear rate significantly reduce, if adopt its solution regeneration hear rate of the hot salt of wormwood decarbonization process of typical B enfield catalysis to be about 1200kcal/Nm 3CO 2(5016kJ/Nm 3CO 2), and the regeneration hear rate≤800kcal/Nm of this technology 3CO 2(3344kJ/Nm 3CO 2), reduce more than 30%.
Description of drawings: accompanying drawing is an embodiment of the invention process flow diagram.In the accompanying drawing, 1-water-and-oil separator I; 2-water-and-oil separator II; 3-decontaminating separator II; 4-cleaner water cooler; 5-water wash column I; 6-decontaminating separator I; 7-water wash column II; 8-decarburization absorption tower; 9-lean solution water cooler; 10-rich solution flash drum; 11-steam boiling device II; 12-normal pressure regenerator column; 13-is by air-breathing cooling separator; The 14-lean solution flash drum; 15-resurgent gases injector; 16-resurgent gases cooling separator; The 17-regenerator column that pressurizes; 18-resurgent gases cooling tower; 19-steam boiling device I; 20-resurgent gases separator; 21-water circulating pump I; 22-water circulating pump II; The 23-semi-leanpump; The 24-lean pump; The 25-condensate pump.
Embodiment:
Below in conjunction with drawings and Examples the present invention is described in detail.
As accompanying drawing, go out the Fischer-Tropsch synthetic tower gas delivery enter decarbonization device behind the liquid product wherein, at first enter water wash column I (5), in the flush away circulation gas after most of oxygen-bearing organic matter and the heavy hydrocarbon of carbon more than 6, in by air-breathing cooling separator (13) with behind the resurgent gases heat exchange recovery heat, send into decarburization absorption tower (8) again, in the absorption tower, remove carbonic acid gas with the decarbonizing solution counter current contact, go out the purified gas process washing separation that the absorption tower touches the mark, refrigerated separation, prevent that gas entrainment salt of wormwood from influencing the fischer-tropsch reaction catalyzer, returns synthesis system then and recycle.Oil that water-and-oil separator I (1) and II (2) will separate and the water that is dissolved with oxygen-bearing organic matter are sent to respectively to handle and are reclaimed.
The rich solution that goes out the absorption tower then flashes off earlier the most of H that is dissolved in the rich solution in rich solution flash drum (10) 2, CO and lighter hydrocarbons, reclaim and use; Enter the top secondary flash distillation of pressurization regenerator column (17) then, come out to have the CO of certain pressure with flash distillation 2Enter resurgent gases injector (15) as spraying power gas suction normal pressure regenerator column (12) with water vapour, the rich solution after the flash distillation is divided into upper and lower two strands at pressurization regenerator column stripping section and enters the normal pressure regenerator column, desorb CO 2After become semi lean solution, pump into the absorption tower hypomere; The solution of pressurization regenerator column stripping section remainder enters steam boiling device I (19) and boils regeneration formation lean solution, have in the lean solution flash drum (14) of lean solution under pressure-fired or vacuum condition of certain temperature, pressure and flash off a large amount of water vapour, the semi lean solution gas of supplying with in the normal pressure regenerator column is proposed regeneration; Because the suction function of injector, two regenerator columns form pressure reduction, make that the solution boiling point produces about 25 ℃ the temperature difference at the bottom of two towers, therefore, the waste heat of steam boiling device I (19) outlet steam water interface can be used for heating semi lean solution once more in steam boiling device II (11), realize that the heat energy classification repeatedly utilizes, and reaches energy-conservation purpose.
Embodiment 1
One is raw material, the stove gas making of usefulness Texaco, employing ferrum-based catalyst, Fischer-Tropsch synthetic pulp state bed reactor with the coal water slurry, concentration of potassium carbonate 28 (m) % is adopted in the circulation gas decarburization, inhibiter Vanadium Pentoxide in FLAKES concentration 5%, the mixture concentration 9% of inorganic activator boric acid, selenous acid, Vanadium Pentoxide in FLAKES; Absorb at the bottom of 90 ℃ of the temperature cats head, tower of operation 115 ℃, pressure 2.7Mpa, CO2 content is 22% in the circulation gas, go out the residual CO2 in absorption tower<0.6%, hydrocarbon consumes<1.0%, the solution absorption ability is about 22Nm3CO2/m3 solution, can satisfy designed decarburizing Fischer-Tropsch synthetic recycle gas requirement, the regeneration hear rate of solution≤3330 kJ/Nm3 CO2.
Embodiment 2
One is raw material, the gas making of usefulness shell coal-powder boiler, employing ferrimanganic composite catalyst, Fischer-Tropsch synthetic pulp state bed reactor with fine coal, concentration of potassium carbonate 26 (m) % is adopted in the circulation gas decarburization, inhibiter Vanadium Pentoxide in FLAKES concentration 5%, the mixture concentration 9% of inorganic activator boric acid, metaantimmonic acid, Vanadium Pentoxide in FLAKES; Absorb at the bottom of 90 ℃ of the temperature cats head, tower of operation 116 ℃, pressure 2.6 Mpa, CO2 content is 20% in the circulation gas, go out the residual CO2 in absorption tower<1.0%, hydrocarbon consumes<0.6%, the solution absorption ability is about 20Nm3CO2/m3 solution, can satisfy designed decarburizing Fischer-Tropsch synthetic recycle gas requirement, the regeneration hear rate of solution≤3330 kJ/Nm3 CO2.
Embodiment 3
One is raw material, the gas making of usefulness lurgi gasifier, employing iron-based composite catalyst, Fischer-Tropsch synthetic pulp state bed reactor with the broken coal, concentration of potassium carbonate 27 (m) % is adopted in the decarburization of circulation gas, inhibiter Vanadium Pentoxide in FLAKES concentration 5%, the mixture concentration 5% of inorganic activator boric acid, telluric acid, organic activator, the mixture concentration in Padil, Methylimidazole and the 2 amino-2 methyl isophthalic acid propyl alcohol is 3%; Absorb at the bottom of 90 ℃ of service temperature cats head, the tower 108 ℃, pressure 2.7Mpa, CO2 content is 19% in the circulation gas, go out the residual CO2 in absorption tower<1.0%, hydrocarbon consumes<0.5%, receptivity is about 29Nm3CO2/m3 solution, satisfies the decarburizing Fischer-Tropsch synthetic recycle gas requirement, solution regeneration hear rate≤3320kJ/Nm3CO2.
Embodiment 4
One is raw material, the gas making of usefulness conversion process, employing metallocene composite catalyst, isothermal tubulation Fischer-Tropsch synthesis device with the associated gas, concentration of potassium carbonate 25 (m) % is adopted in the decarburization of circulation gas, inhibiter Vanadium Pentoxide in FLAKES concentration 5%, the mixture concentration 5% of inorganic activator boric acid, selenous acid, organic activator hydroxyethyl diamine, 2 piperidines alcoholic acid mixture concentrations are 3%; Absorb at the bottom of 90 ℃ of service temperature cats head, the tower 109 ℃, pressure 2.8Mpa, CO2 content is 11% in the circulation gas, go out the residual CO2 in absorption tower<1.0%, hydrocarbon consumes<0.5%, receptivity is about 26Nm3CO2/m3 solution, satisfies the decarburizing Fischer-Tropsch synthetic recycle gas requirement, solution regeneration hear rate≤3320kJ/Nm3 CO2.
Embodiment 5
One is raw material, the gas making of usefulness conversion process, employing composite catalyst, isothermal tubulation Fischer-Tropsch synthesis device with the Sweet natural gas, concentration of potassium carbonate 25 (m) % is adopted in the decarburization of circulation gas, inhibiter Vanadium Pentoxide in FLAKES concentration 5%, the mixture concentration 5% of inorganic activator boric acid, selenous acid, the mixture concentration of organic activator 2-ethylaminoethyl alcohol, 2 amino-2 methyl isophthalic acid propyl alcohol is 3%; Absorb at the bottom of 90 ℃ of service temperature cats head, the tower 108 ℃, pressure 2.6Mpa, CO2 content is 10% in the circulation gas, go out the residual CO2 in absorption tower<1.0%, hydrocarbon consumes<0.4%, receptivity is about 24Nm3CO2/m3 solution, satisfies the decarburizing Fischer-Tropsch synthetic recycle gas requirement, solution regeneration hear rate≤3344kJ/Nm3CO2.

Claims (10)

1. the solvent of a removing carbon dioxide from Fischer-Tropsch synthesis circulation gas, it is characterized in that aqueous solution composition comprises salt of wormwood, inhibiter, activator, activator is mineral compound or mineral compound and organic compound, salt of wormwood weight concentration 10~40%, the weight concentration 1~10% of inhibiter Vanadium Pentoxide in FLAKES, inorganic activator is a kind of or its mixture in boric acid, selenous acid, metaantimmonic acid, telluric acid, the Vanadium Pentoxide in FLAKES, weight concentration 1~30%; Organic activator is a kind of or its mixture in Padil, hydroxyethyl diamine, diethanolamine, quadrol, Diethylenetriaminee (DETA), dihydroxy ethyl quadrol, imidazoles, Methylimidazole, tetramethylene sulfone, N-cyclohexyl 1,3 propylene diamine, 2 amino-2 methyl isophthalic acid propyl alcohol, dimethylamino-2-propyl alcohol, 2 piperidines ethanol, the 2-ethylaminoethyl alcohol, and weight concentration is 0~20%.
2. solvent as claimed in claim 1 is characterized in that concentration of potassium carbonate 20~30%, density of corrosion inhibitor 2~7%, inorganic activation agent concentration 2~20%, organic active agent concentration 0~10%.
3. the method for a removing carbon dioxide from Fischer-Tropsch synthesis circulation gas is characterized in that increasing in the water wash column flush away circulation gas most of oxygen-bearing organic matter and the heavy hydrocarbon of carbon 6 or more also by the waste water treatment and reclamation organism in the absorption flow process of routine; Solution absorption adopts and activates solution of potassium carbonate according to claim 1, and the pressure that absorbs operation is that circulation gas separates back pressure, and pressure is 1.0~10.0Mpa, absorbs 60~110 ℃ of cat head service temperatures, and column bottom temperature is controlled at 90~125 ℃; Rich solution after the absorption reclaims most of H by flash distillation 2, CO and lighter hydrocarbons; The pressure swing regeneration technology is adopted in the desorb of solution.
4. method as claimed in claim 3, it is characterized in that washing pressure is that circulation gas separates back pressure, and pressure is 1.0~10.0Mpa, and water temperature is controlled at 0~100 ℃, and water/gas ratio is controlled at 1m 3Water: 100~10000Nm 3Gas.
5. method as claimed in claim 4 is characterized in that water temperature is controlled at 20~80 ℃, and water/gas ratio is controlled at 1m 3Water: 300~3000Nm 3Gas.
6. method as claimed in claim 3 is characterized in that absorbing 80~100 ℃ of cat head service temperatures, and column bottom temperature is controlled at 100~120 ℃.
7. method as claimed in claim 3 is characterized in that adopting the rich solution flash drum on stream, flashes off the most of H that is dissolved in the rich solution 2, CO and lighter hydrocarbons, reclaim and use, the working pressure of rich solution flash drum is in absolute pressure 0.1~1.6Mpa scope, service temperature is at 70~125 ℃.
8. method as claimed in claim 7, the pressure that it is characterized in that the rich solution flash drum is in absolute pressure 0.4~1.1Mpa scope, and service temperature is at 90~120 ℃.
9. method as claimed in claim 3 is characterized in that the pressure swing regeneration power-saving technology is adopted in the desorb of solution, the CO that utilizes the flash distillation of pressurization regeneration overhead to come out 2With water vapour as power, by " subsonic speed injector " suction normal pressure regenerator column, form pressure reduction between two towers, pressurization regeneration overhead pressure-controlling is at absolute pressure 0.15~0.35Mpa, normal pressure regeneration overhead pressure-controlling absolute pressure 0.05~0Mpa or 0~-0.05Mpa, make that the solution boiling point produces 15~30 ℃ the temperature difference at the bottom of two towers.
10. method as claimed in claim 9, the regeneration overhead pressure-controlling that it is characterized in that pressurizeing be at absolute pressure 0.17~0.28Mpa, normal pressure regeneration overhead pressure-controlling absolute pressure 0.04~-0.03Mpa, make that the solution boiling point produces 20~25 ℃ the temperature difference at the bottom of two towers.
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