CN103497801B - A kind of technique utilizing carbon black tail gas to prepare synthetic natural gas - Google Patents
A kind of technique utilizing carbon black tail gas to prepare synthetic natural gas Download PDFInfo
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- CN103497801B CN103497801B CN201310483191.7A CN201310483191A CN103497801B CN 103497801 B CN103497801 B CN 103497801B CN 201310483191 A CN201310483191 A CN 201310483191A CN 103497801 B CN103497801 B CN 103497801B
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Abstract
The present invention discloses a kind of technique utilizing carbon black tail gas to prepare synthetic natural gas, and carbon black tail gas is through air blast, dedusting, and CO converts, and the CO in carbon black tail gas and water vapour convert and generates H
2and CO
2, then methanation reaction is carried out after cooling de-watering, desulfurization, supercharging, after cooling de-watering drying, carry out methane concentrate and get final product.Beneficial effect of the present invention: (1) proposes the carbon black tail gas synthetic natural gas technique of industrial scale first, reaches the recycling of industrial discharge gas, energy-saving and emission-reduction, turns waste into wealth effect; (2) heat of carbon black tail gas own, water vapour and sulfide is utilized, without the need to heating, without the need to make up water steam, without the need to cooling, simple flow; (3) amount of heat is released in conversion and methanation, by appropriate design, realizes each operating unit heat integration and utilizes, without the need to extraneous supplemental heat source, go back by-product high-quality steam; (4) can production high purity methane product, as CNG, LNG or gas after process, also can industrial chemicals be made.
Description
Technical field
The present invention relates to the technique of preparation synthetic natural gas, especially a kind of technique utilizing carbon black tail gas to prepare synthetic natural gas.
Background technology
Carbon black is that the hydrocarbon polymer of gaseous state or liquid state carries out incomplete combustion under the condition of lack of air or the decolorizing carbon generated is decomposed in hot tearing, for loose, light weight and superfine black powder material, there is high dispersion, be insoluble to all kinds of SOLVENTS, relative density 1.8 ~ 2.1.Its composition mainly elemental carbon, and containing a small amount of oxygen, hydrogen and sulphur and other impurity and moisture etc., its crystallite has meta anthracite structure.
Carbon black is mainly used as strengthening agent and the filler of rubber, and rubber grade carbon black accounts for 90% of carbon black total amount, and wherein about 70% for Tire production, and the carbon black consumption of about 80% is used for automotive industry.In addition, also the tinting material of ink and the ultravioletlight screening agent of plastics is used as.At other goods many, as in electrode, drying battery, resistor, explosive, makeup and rubbing paste, carbon black is also important auxiliary agent.
Within 2012, global carbon black demand reaches 1,160 ten thousand t, estimates that in the five-year, world's carbon black output can cumulative year after year 4.6%.China's carbon black output in 2012 reaches 3,760,000 tons, demand about 3,850,000 tons, and increased by 680,000 tons than 2011, speedup reaches 21%.2012-2015 domestic carbon black output compound speedup, about 11%, is expected to reach 5,400,000 tons for 2015.
What in the production method of carbon black, technology was more ripe has channel process, oven process and pyrolysis method.Wherein Audit For Process yield is the highest, energy consumption is minimum, and its output accounts for more than 95% of carbon black ultimate production.Audit For Process carbon black raw oil is divided three classes: the fluid catalytic cracking decant oil of refinery by-product, ethylene bottom oil and coal tar.Europe and U.S.'s carbon black raw oil are based on clarified oil, and China's carbon black feed stock is based on coal tar and ethylene bottom oil.
Audit For Process production of carbon black flow process is: the oil fuel after dehydration boosts through oil pump, is warmed up to 110 ~ 130 DEG C in steam jacket oil pipe, then through oil nozzle atomised jet in Reaktionsofen.Freezing air enters air preheater through orifice-plate flowmeter and is heated to 350 ~ 400 DEG C and enters after fuel nozzle fully mixes with mist of oil and enter in Reaktionsofen.Under the heating of oil fuel, Reaktionsofen temperature maintains 1300 ~ 1600 DEG C.Stock oil at these elevated temperatures cracking generates carbon black and contains CO
2, H
2o, N
2, superfluous O
2and a small amount of NOx, SOx and H
2the high-temperature flue gas that S etc. about 1700 DEG C.After flue gas leaves Reaktionsofen, spray into water quick cooling to 900 ~ 1000 DEG C immediately, with termination reaction.Flue gas after chilling is cooled to 600 ~ 650 DEG C through two-stage waste heat boiler again, enter shell and tube cooler subsequently, flue gas is made to be cooled to 450 ~ 550 DEG C, enter three grades of air preheaters, flue gas and air countercurrent flow, flue-gas temperature drops to 200 ~ 250 DEG C, sends into three-stage cyclone separator, isolate most of carbon black, tail gas enters in pulse bag filter after air cooler is cooled to 80 ~ 140 DEG C.Tail gas is pumped to smoke stack emission by vacuum fan after filtering.By the carbon black collected in cyclonic separator and pulse bag filter, sent in wet granulator by air-transport system.Wet dustless carbon black in dry, then sent into basin, is transported in bulk or packed mode in roundabout drier.
Audit For Process often produces 1 ton of carbon black, produces 3500m
3dust-containing tail gas.By China's carbon black output in 2012 3760000 tons, carbon black tail gas is more than 13,000,000,000 m
3.Current carbon black enterprise all processes carbon black tail gas, and it utilizes the heat of high temperature mainly reclaimed wherein, and a large amount of tail gas directly enters in air, causes serious environmental pollution.
Up to now, domestic also without report and the use of carbon black tail gas synthetic natural gas.
Chinese invention patent application 102120120A discloses a kind for the treatment of process of carbon black tail gas.With water, carbon black tail gas is washed, removing steam and part H
2s gas, then after activated alumina drying, adopt temperature swing absorption unit to remove H with gac or carbonaceous molecular sieve
2s and SO
2, then the N of concentration 99% is obtained by Pressure Swing Adsorption
2, remaining waste gas is for burning.
China's conventional gas stock number is about 35-38 trillion Nm
3, account for 2% of world's total amount; Wherein mining resources amount 10-12 trillion Nm
3, Sweet natural gas residual recoverable reserves is only equivalent to 6% of world average level per capita.Sweet natural gas is as a kind of high-quality clean energy, and the proportion at present in China's primary energy source consumption is only 3.9%, well below the mean level (ML) in the world 23.7%.
Along with the development of urbanization, China's natural gas consumption speedup exceedes output speedup, and import volume increases year by year.Within 2012, China's natural gas consumption reaches 1,471 hundred million Nm
3, inlet natural gas 39,400,000,000 Nm
3.According to Development Research Center of the State Council's prediction, 2,600 hundred million Nm will be increased to China's natural gas consumption in 2015
3, need import 75,000,000,000 Nm
3; To the year two thousand twenty consumption more than 3,000 hundred million Nm
3, about have 40% dependence on import when the time comes.Country encourages the development and production of Unconventional forage in recent years, comprises the research and development carried out coal-seam gas, refuse embedded gas, shale gas, coke(oven)gas etc. and prepare Unconventional forage, to make up the deficiency of Natural Gas Demand.
Summary of the invention
The object of the invention is on the basis of CO sulfur-resisting transformation technology, methanation technology and methane concentrate technology, provide a kind of carbon black tail gas being suitable for industrial scale applications to prepare the technique of synthetic natural gas.
For achieving the above object, the present invention is by the following technical solutions:
Present invention process is by raw material carbon black tail gas through air blast, dedusting, carries out CO conversion, and the CO in carbon black tail gas and water vapour convert and generates H
2and CO
2(reaction formula 1), through cooling de-watering, desulfurization, carries out methanation reaction after supercharging, then carry out methane concentrate after cooling de-watering drying, obtain synthetic natural gas.
Wherein, preferably can carry out decarburization in above-mentioned steps after desulfurization or carry out desulfurization and decarburization simultaneously, namely carry out methanation reaction (reaction formula 2), cooling de-watering drying, concentrate through being pressurized to 2.0-3.0MPa and get final product.
The whole reaction process of above-mentioned technique is:
CO+H
2o → CO
2+ H
2(reaction formula 1)
CO+3H
2→ CH
4+ H
2o(reaction formula 2)
For making water vapor still be in gaseous state, unstripped gas carbon black tail gas temperature of the present invention needs maintenance to be greater than 100 DEG C.Record in patent application 102120120A, carbon black tail gas consist of CO:9 ~ 13%, H
2: 12%, CO
2: 2 ~ 3%, N
2: 36 ~ 38%, H
2o:36 ~ 40%, H
2s:250 ~ 800mg/m
3simultaneously also containing SO
2, SO
3deng impurity.
The above-mentioned dedusting to raw material carbon black tail gas can adopt ceramic filter dedusting or adopt bag-type dust, for overcoming systemic resistance, gas blower before dedusting, is adopted to carry out supercharging to carbon black tail gas, different according to method for dust removal, the size of required supercharging also differs, and is generally 50-80kpa.Ceramic filter dedusting is by carbon black tail gas after porcelain filter, and gas dust content can be down to 5 ~ 10mg/Nm
3, ceramic filter and blowback hocket, wherein, the temperature of carbon black tail gas on the working temperature of porcelain filter without impact; Bag-type dust is sack cleaner carbon black tail gas being entered multiple stage parallel connection, and the carbon black tail gas dustiness after dedusting can drop to 50mg/Nm
3below.
Through the carbon black tail gas of dedusting, enter CO conversion, carry out transformationreation, transformationreation refers under catalyst action, and CO and water vapour react and generates CO
2and H
2, the CO amount that in carbon black tail gas, the amount of water vapour relatively wherein contains is enough, without the need to make up water.Reacting condition equation is:
CO+H
2o → CO
2+ H
2(reaction formula 1)
CO conversion is the key link during Coal Chemical Industry is produced, and is technological process important in synthetic ammonia, methyl alcohol and process for making hydrogen.Converted by CO, while the most of CO of consumption, convert available gas H to
2, for downstream synthesis provides H
2raw material.The degree of depth of transformationreation is by CO and H in carbon black tail gas
2amount determine.Preferably, requiring by controlling temperature of reaction and reaction times, making the H in mixed gas after conversion
2amount meets follow-up methanation to H
2demand.Preferred, the amounts of hydrogen sum that the amounts of hydrogen in unstripped gas and transformationreation generate, can by CO completely consumed in follow-up methanation, that is, and the total H after conversion in gas
2amount is at least three times of remaining CO tolerance after conversion.
Preferably, when conversion process is large-minded, when causing reaction bed temperature higher than catalyzer allowable temperature, the mode of the classification charging multi-stage transformation that this area can be adopted general is to complete CO conversion.
More specifically, when loaded catalyst is certain, by regulating the air input entering shift-converter, shift-converter is made to import and export the temperature difference between 50-70 DEG C, gas residence time is 30-50s, makes the conversion degree of CO reach 42-52%, thus reaches the degree of depth controlling transformationreation.If CO and H in raw material
2amount and patent application 102120120A in record variant, adopt identical control method, make the total H in gas after conversion
2amount is at least three times of remaining CO tolerance after conversion.
Above-mentioned conversion adopts sulfur resistant conversion process well known in the art, preferred low temperature sulfur tolerant shift, conversion inlet air temperature 200 DEG C-250 DEG C, transformationreation is thermopositive reaction, the air preheat after conversion can be utilized to convert raw material air inlet, also the high-temperature gas after conversion can be used as other purposes, initial carbon black tail gas air inlet can utilize the original High Temperature Gas heat exchange in carbon black plant to heat.
Mixed gas after CO conversion enters desulphurization system and carries out desulfurization after cooling de-watering, as mentioned above, preferably can carry out decarburization after desulfurization or carry out desulfurization and decarburization simultaneously, wherein more preferably carry out desulfurization and decarburization simultaneously, wet desulphurization decarburization can be adopted, preferred chemical solvents alcohol amine absorption process, the preferred MEA(thanomin of absorption agent), DGA(di-alcohol diamines), DEA(diethanolamine), DIPA(diisopropanolamine (DIPA)) and MDEA(methyldiethanolamine).While adopting the advantage of alkanolamine solution absorption process to be desulfurization, CO
2be removed in the lump, independent decarbonation process can be dispensed in subsequent technique.After desulfurization, total S content is lower than 1mg/m
3, CO
2content is lower than 50mg/m
3.
Gas boosting after desulfurization and decarburization to 2.0-3.0MPa, and carries out methanation after preheating, under catalyst action, and CO and the H in gas
2reaction generates CH
4and water.
Described methanation reaction equation is:
CO+3H
2→ CH
4+ H
2o(reaction formula 2)
Methanation adopts a kind of methanation technology utilized in the method 1919985A of preparing synthesis gas from coke-oven gas of the Chinese invention patent of the applicant, gas inlet temperature is preferably 280 DEG C-320 DEG C, reaction pressure is 2.0-3.0MPa, methane turns to thermopositive reaction, the hot gas preheating material air inlet after methanation can be utilized, all right byproduct steam, the steam of institute's by-product can be used as other purposes of this technique, also can be used for generating.When methanation process is large-minded, when causing reaction bed temperature higher than catalyzer allowable temperature, the mode of the multistage methanation of classification charging can be adopted to realize, technology disclosed in a kind of method 101508922A for preparing synthesis gas from coke-oven gas of the Chinese invention patent of the applicant can be adopted.
Control through CO transformationreation, carry out in the gas of methanation reaction, CO and H
2amount be coupling, by the consumption of the overwhelming majority in methanation reaction.After methanation reaction, CO and H in carbon black tail gas
2be converted to CH
4and water, also containing original N
2, trace amounts of CO and H
2.
Through methanation reaction mixed gas out through cooling, carry out drying after isolating liquid water, preferred solid absorption desiccating method, siccative preferred molecular sieve or silica gel, mixed gas after drying carries out methane concentrate can obtain synthetic natural gas.
Methane concentrate adopts the method be separated by CH
4be separated from mixed gas and collect, the preferred PSA method (pressure swing adsorption process) of separation method or low temperature processing.For low temperature processing, before requiring to enter low ternperature separation process, again 4.0-5.0MPa is pressurized to gas, ensures CO in gas simultaneously
2volumn concentration is lower than 50ppm, and volume of water percentage composition is lower than 10ppm, and this is easily realize by above-mentioned desulfurization and decarburization and drying and dehydrating.
Above-mentioned pressure swing adsorption process concentrate methane, can refer to the method in the Chinese invention patent 85103557A " in pressure swing adsorption process enrichment coal mine mash gas methane " of the applicant's proposition, also can refer to pressure swing adsorption process conventional in other prior aries.
Above-mentioned low temperature processing is a kind of liquefaction fractionation process, can refer to the method in the Chinese patent 1718680A " low ternperature separation process concentrate methane technology " of the applicant, also can refer to other low ternperature separation process methanol method of the prior art.
Under the guidance of above-mentioned principle, carbon black tail gas is through dust-removal system, dust-removal system is preferably porcelain filter or cloth envelop collector, after enter CO shift-converter, preferably sulfur-tolerant water gas shift device, be more preferably low temperature sulfur tolerant shift reactor, enter the inlet air temperature 200 DEG C-250 DEG C of shift-converter, by controlling the air input of shift-converter, the conversion degree of CO is made to reach 42-52%, carbon black tail gas is after conversion, transformationreation liberated heat is utilized to heat the air inlet of shift-converter, the initial carbon black tail gas air inlet entering shift-converter can utilize the original High Temperature Gas heat exchange in carbon black plant to heat.After condensation, gas-water separation, desulphurization system or decarbonization desulfurization system is entered from shift-converter mixed gas out, preferably wet desulphurization decarbonization system, be more preferably chemical solvents hydramine Absorption Desulfurization decarbonization system, be in particular and enter from bottom, absorption tower after condensation, gas-water separation from shift-converter mixed gas out, pass through absorption tower from bottom to top; Alkanolamine solution (lean solution) after regeneration enters from top, absorption tower, and pass through absorption tower, the alkanolamine solution of countercurrent flow fully contacts in absorption tower with mixed gas, the H in gas
2s, SO
2, SO
3and CO
2absorbed.The alkanolamine solution absorbing sour gas is called rich solution, to regenerator column thermal regeneration.After regeneration, sour gas parses from alkanolamine solution rich solution, collection and treatment after cooling.Alkanolamine solution after regeneration is called lean solution, and the lean solution gone out bottom regenerator column enters top, absorption tower and recycles after cooling.Gas after desulfurization and decarburization is through being pressurized to 2.0-3.0MPa, and enter methanation reaction system after preheating and carry out methanation, the gas temperature entering methanation reaction system is preferably 280 DEG C-320 DEG C, methane turns to thermopositive reaction, the air inlet of the hot gas preheating methanation reaction system after methanation can be utilized, all right byproduct steam, go out the mixed gas of methanation reaction system through cooling, dehumidification system is entered after isolating liquid water, dehumidification system is made up of two towers, a wherein use, another regeneration, siccative preferred molecular sieve or silica gel, mixed gas is through entering methane upgrading system after drying, finally obtained synthetic natural gas.Methane concentrate adopts PSA method (pressure swing adsorption process) or low temperature processing.For low temperature processing, enter cryogenic separation system after 4.0-5.0MPa being pressurized to again to gas before requiring to enter low ternperature separation process and isolate methane, obtained natural gas liquids (LNG).
The synthetic natural gas obtained after adopting PSA method concentrate can obtain compressed natural gas (CNG) or gas through compressing further.
Research shows, containing the CO of 9-13% in carbon black tail gas, simultaneously containing have an appointment 40% water vapour, the H of 9-13% can be obtained after conversion
2, H
2methane can be obtained, 13,000,000,000 m that China discharges every year with CO methanation
3carbon black tail gas, can obtain 1,000,000,000 m through recycling
3pure methane product.
The synthetic natural gas calorific value obtained through the present invention is greater than 36MJ/m
3, carbonic acid gas is less than 100ppm, and total sulfur is lower than 10mg/m
3, its index is obviously better than the regulation in GB17820-2012 " Sweet natural gas ", and the quality index of the compressed natural gas that compression is obtained is also obviously better than the regulation in GB18047-2000 " compressed natural gas " further.
Beneficial effect of the present invention is:
(1) proposing first can the technique of carbon black tail gas synthetic natural gas of industrial scale, utilizes the monotechnics of existing maturation, reliability is high, advantage that heat utilization ratio is high, reaches the recycling of industrial discharge gas, energy-saving and emission-reduction, the effect that turns waste into wealth;
(2) utilize the heat of carbon black tail gas itself, water vapour and sulfide, directly enter the reaction of sulfur-tolerant water gas shift device generation low temperature sulfur tolerant shift, without the need to heating, without the need to make up water steam, without the need to cooling, simple flow;
(3) conversion and methanation all release amount of heat, by the appropriate design to whole technical process, can realize the comprehensive utilization of each operating unit heat, without the need to extraneous supplemental heat source, and also can by-product high-quality steam;
(4) carbon black tail gas can produce highly purified methane product after this technique, after treatment as CNG, LNG or gas for sale, also can be used as Chemical Manufacture raw material.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the process flow diagram of the embodiment of the present invention 1.
Fig. 2 is the process flow diagram of the embodiment of the present invention 2.
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets (comprising any accessory claim, summary and accompanying drawing), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Embodiment 1
Produce carbon black process flow process according to current Audit For Process, after three-stage cyclone separator and pulse bag filter, carbon black tail gas temperature is down to 80 ~ 140 DEG C, and this gas is unstripped gas of the present invention.
From the carbon black tail gas (composition is in table 1) of about 140 DEG C, carbon black plant through blower to 80kpa, after cloth envelop collector dedusting, enter transformationreation preheater and be heated to 200 DEG C, transformationreation gas temperature out is 250 DEG C, gas residence time 50s, this transformationreation preheater utilizes transformationreation liberated heat to heat transformationreation air inlet, enter sulfur-tolerant water gas shift device afterwards, under conventional sulfur-resistant transformation catalyst effect, in gas 42% CO and water vapour generation sulfur-tolerant water gas shift (see reaction formula 1).The reaction initial stage, utilize carbon black plant's high-temperature gas or the air inlet of electric heater heating raw, after reaction starts, utilize out the high-temperature gas mixture body preheating material air inlet of shift-converter, the mixed gas main component going out to convert preheater is CO, CO
2, H
2, N
2and water vapour, the rich solution that this hot gas is used for heating desulfurization and decarburization reclaims heat further.Mixed gas through cooling enters to enter after liquid water isolated by air water separator after water cooler is chilled to normal temperature and enters decarbonization desulfurization system, and what the present embodiment was selected is chemical solvents alcohol amine absorption process decarbonization desulfurization system, and alkanolamine solution selects MEA(thanomin).
The mixed gas going out shift-converter enters from bottom, absorption tower after condenser, air water separator, passes through absorption tower from bottom to top; MEA solution (lean solution) after regeneration enters from top, absorption tower, and pass through absorption tower, the MEA of countercurrent flow fully contacts in absorption tower with mixed gas, the H in gas
2s, SO
2, SO
3and CO
2absorbed.
The MEA absorbing sour gas is called rich solution, to regenerator column thermal regeneration.After regeneration, sour gas parses from MEA rich solution, collects after cooling.
MEA after regeneration is called lean solution, and the lean solution gone out bottom regenerator column enters top, absorption tower and recycles after cooling.
After desulfurization and decarburization, mixed gas is pressurized to 2.0MPa, and enter methanation reaction system after being heated to 280 DEG C, the reaction initial stage, utilize carbon black plant's high-temperature gas or the air inlet of electric heater heating raw, after reaction starts, utilize out the high-temperature gas mixture body preheating material air inlet of methanator, under the methanation catalyst effect in 200810046429.9, methanation reaction occurs, CO and H wherein
2there is methanation reaction and generate methane and water (see reaction formula 2).
Methanation reaction system adopts separate unit methanator, arranges waste heat boiler and reclaim heat, byproduct steam after methanation reaction.
The mixed gas main component going out methanation reaction system is CH
4, N
2and water vapour, separately there is a small amount of unreacted CO and H completely
2.This mixed gas enters and to enter after air water separator isolates liquid water after water cooler is chilled to normal temperature, then enters dehumidification system dehydration.
Dehumidification system is made up of two towers, wherein a use, and another regeneration, molecular sieve selected by siccative, and mixed gas enters PSA concentrate methane system after drying.
PSA system is made up of two portions, i.e. PSA1, PSA2.
PSA1 is by being the PSA system be made up of 10 adsorbers and a series of time variable control valve, and the gas from moisture eliminator enters PSA1 and concentrates methane.In PSA system, every platform adsorber different time experience successively absorption (A), multistage all fall (EiD), displacement (RP), inverse put (D), find time (V), multistage all rise (EiR), fill eventually (FR); By the methane component of adsorbing by inverse put, find time to obtain product synthetic natural gas, adsorption tower completes desorption process simultaneously.Absorption waste gas enters PSA2 again and concentrates methane.Inverse put and the gas major part of finding time export battery limit (BL) as product synthetic natural gas, and small part is forced into after 0.15MPa as displacement gas.Displacement waste gas is sent into feed gas compressor entrance and is entered PSA1 more after compression.
PSA2 is by being the PSA system be made up of 8 adsorbers and a series of time variable control valve.Absorption waste gas from PSA1 enters PSA2 concentrated methane again, in PSA2 system, every platform adsorber different time experience successively absorption (A), multistage all fall (EiD), inverse put (D), find time (V), multistage all rise (EiR), fill eventually (FR); By the component of adsorbing by inverse put with find time to obtain desorb, after inverse put and the incoming stock air compressor supercharging of the gas of finding time, enter PSA1 system.
Adopt the synthetic natural gas methane concentration 93.03% that this technique is obtained, calorific value 36MJ/m
3.
The composition of table 1 raw material carbon black tail gas
Each operation material balance of table 2 embodiment 1
embodiment 2
From the carbon black tail gas (composition is in table 2) of about 101 DEG C, carbon black plant after gas-water separation, through blower 50kpa, enter porcelain filter, 5 minutes ceramic filter time, blowback 1 minute, filter and hocket with blowback.After porcelain filter, gas dust-laden is down to 5 ~ 10mg/Nm
3.
Gas after dedusting enters transformationreation preheater and is heated to 250 DEG C, enter shift-converter afterwards, catalyzer (the QSC-3 sulfur-resistant transformation catalyst of certain companies market domestic) effect under, in gas 52% CO and water vapour generation sulfur-tolerant water gas shift (see reaction formula 1).Transformationreation gas temperature out is 320 DEG C, gas residence time 30s, and the startup of transformationreation is identical with embodiment 1 with Btu utilization mode.Mixed gas through cooling enters to enter after liquid water isolated by air water separator after water cooler is chilled to normal temperature and enters chemical solvents alcohol amine absorption process decarbonization desulfurization system, this decarbonization desulfurization system and process substantially the same manner as Example 1, just alcohol amine solvent selects DGA(di-alcohol diamines), also can adopt DEA(diethanolamine).
Mixed gas after desulfurization and decarburization is pressurized to 3.0MPa, and enter methanation reaction system after being heated to 320 DEG C, the reaction initial stage, utilize carbon black plant's high-temperature gas or the air inlet of electric heater heating raw, after reaction starts, utilize out the high-temperature gas mixture body preheating material air inlet of methanator, under catalyst action disclosed in patent of invention 201110144803.0, methanation reaction occurs, CO and H wherein
2there is methanation reaction and generate methane and water (see reaction formula 2).Methanation reaction system is made up of two methanators, arranges waste heat boiler and reclaim heat, byproduct steam after every grade of methanation reaction.
The mixed gas main component going out methanation reaction system is CH
4, N
2and water vapour, another also have a small amount of unreacted CO and H completely
2.This mixed gas enters to enter after water cooler is chilled to normal temperature after liquid water isolated by air water separator and enters dehumidification system dehydration.
Dehumidification system and process substantially the same manner as Example 1, silica gel selected by siccative.
Mixed gas enters low ternperature separation process methane upgrading system after being pressurized to 4.0MPa after drying, and detailed process is:
Mixed gas is successively through precool heat exchanger device, main heat exchanger and liquefaction heat exchanger after drying, and temperature reduces gradually, then through rectifying tower evaporator cools to ~-132 DEG C, enter after throttling in the middle part of rectifying tower and be separated.Gas phase is as the gas risen, and a small amount of gas is condensed and does phegma in the condenser of rectifying tower tower top, is heated by vaporizer at the liquid of rectifying tower bottom part, and gas rises and phegma heat and mass.From rectifier bottoms liquid LNG product out, cross the LNG storage tank that cold rear cooling box sends into user crossing in cold heat exchanger; Rectifying tower ejects the residual gas that comes first through cold heat exchanger re-heat, then is followed successively by liquefaction heat exchanger and main heat exchanger provides cold, sends ice chest as moisture eliminator resurgent gases after re-heat.
Nitrogen is adopted to provide cold as cryogen.Nitrogen enters in precool heat exchanger device and cools after nitrogen compressor supercharging, cooling, enters after main heat exchanger is cooled to-62 DEG C and divides two-way; One tunnel enters booster expansion turbine, returns liquefaction heat exchanger after adiabatic expansion; After throttling valve reducing pressure by regulating flow, first provide cold to rectifying tower top condenser after cooling is continued on another road, then with expansion gas for main heat exchanger provides cold, after cooling box, enter circulating nitrogen gas compressor, forms a closed expander refrigeration and circulate.
Adopt the synthetic natural gas methane concentration 96.23% that this technique is obtained, calorific value 38.3MJ/m
3.
The composition of table 3 raw material carbon black tail gas
Each operation material balance of table 4 embodiment 2
embodiment 3
From the carbon black tail gas (see table 5) of about 120 DEG C, carbon black plant through blower to 70kpa, enter sack cleaner dedusting, enter transformationreation preheater and be heated to 250 DEG C, enter shift-converter afterwards, under catalyzer (import K8-11 transformation catalyst) effect, in gas 48% CO and water vapour generation transformationreation (see reaction formula 1), transformationreation gas temperature out is 310 DEG C, gas residence time 40s, hot gas after conversion enters conversion preheater preheats material mixed gas, and the startup of transformationreation is identical with embodiment 1 with Btu utilization mode.The mixed gas main component going out transformationreation system is CO, CO
2, H
2, N
2and water vapour, this mixed gas enters to enter after liquid water isolated by air water separator after water cooler is chilled to normal temperature and enters chemical solvents alcohol amine absorption process decarbonization desulfurization system, decarbonization desulfurization system and process substantially the same manner as Example 1, but alcohol amine solvent selects DIPA(diisopropanolamine (DIPA)), also can select MDEA(methyldiethanolamine).
After desulfurization and decarburization, mixed gas is pressurized to 2.5MPa, and enters methanation reaction system after being heated to 300 DEG C, under methanation catalyst effect disclosed in patent of invention 200810046429.9, methanation reaction occurs, CO and H wherein
2there is methanation reaction and generate methane and water (see reaction formula 2).The reaction initial stage, utilize carbon black plant's high-temperature gas or the air inlet of electric heater heating raw, reaction utilizes out the high-temperature gas mixture body preheating material air inlet of methanator after starting.Methanation reaction system is made up of three methanators, arranges waste heat boiler and reclaim heat, byproduct steam after every grade of methanation reaction.
The mixed gas main component going out methanation reaction system is CH
4, N
2and water vapour, another also have a small amount of unreacted CO and H completely
2.This mixed gas enters to enter after liquid water isolated by air water separator after water cooler is chilled to normal temperature and enters dehumidification system, and drying process is identical with embodiment 1.
Mixed gas enters low ternperature separation process methane upgrading system after drying, and detailed process and embodiment 2 are together.
Adopt the synthetic natural gas methane concentration 98.62% that this technique is obtained, calorific value 39.3MJ/m
3.
The composition of table 5 raw material carbon black tail gas
Each operation material balance of table 6 embodiment 3
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (8)
1. utilize carbon black tail gas to prepare a technique for synthetic natural gas, it is characterized in that, raw material carbon black tail gas, through air blast, dedusting, carries out CO conversion, and the CO in carbon black tail gas and water vapour convert and generates H
2and CO
2, through cooling de-watering, desulfurization, carry out methanation reaction after supercharging, then carry out methane concentrate after cooling de-watering drying, obtain synthetic natural gas, the temperature of described raw material carbon black tail gas is greater than 100 degree; Pressure of blast 50-80kPa;
Wherein, described CO conversion adopts low temperature sulfur tolerant shift, conversion inlet air temperature 200 DEG C-250 DEG C, conversion process pressure is 2.0-3.0MPa, carbon black tail gas is after conversion, utilize transformationreation liberated heat to heat transformationreation air inlet, initial carbon black tail gas air inlet utilizes the original High Temperature Gas heat exchange in carbon black plant to heat;
The gas inlet temperature of described methanation reaction is 280 DEG C-320 DEG C, and the pressure of methanation reaction is 2.0-3.0MPa, utilizes the hot gas preheating material air inlet after methane reaction, or for byproduct steam;
Described methane concentrate adopts pressure swing adsorption process concentrate or low temperature processing concentrate; During described employing low temperature processing concentrate, enter the gas boosting of cryogenic separation system to 4.0-5.0MPa, CO in gas
2volumn concentration is lower than 50ppm, and the volumn concentration of water is lower than 10ppm.
2. technique as claimed in claim 1, is characterized in that, described dedusting adopts ceramic filter dedusting or adopts bag-type dust; Ceramic filter dedusting is by carbon black tail gas after porcelain filter, and pottery frit and blowback hocket; Bag-type dust is sack cleaner carbon black tail gas being entered multiple stage parallel connection.
3. technique as claimed in claim 1, is characterized in that, described CO conversion adopts the mode of classification charging multi-stage transformation.
4. technique as claimed in claim 3, is characterized in that, the CO transformationreation of described carbon black tail gas, by controlling temperature of reaction and reaction times, makes the H in mixed gas after conversion
2amount meets follow-up methanation to H
2demand, the total H after conversion in gas
2amount is at least three times of remaining CO tolerance after conversion.
5. technique as claimed in claim 4, is characterized in that, regulate CO transformationreation air input, make the import and export temperature difference of shift-converter be 50-70 DEG C, gas residence time is that the conversion degree of 30-50s, CO reaches 42-52%.
6. technique as claimed in claim 1, it is characterized in that, mixed gas after CO conversion enters desulphurization system and carries out desulfurization after cooling de-watering, decarburization or the decarburization when desulfurization after desulfurization, adopt chemical solvents alcohol amine absorption process in wet desulphurization decarburization, absorption agent is thanomin, di-alcohol diamines, diethanolamine, diisopropanolamine (DIPA) and methyldiethanolamine.
7. technique as claimed in claim 1, is characterized in that, described methanation adopts the multistage methanation of classification charging.
8. technique as claimed in claim 1, is characterized in that, described drying adopts solid absorption desiccating method, and siccative is molecular sieve or silica gel.
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| CN105086526A (en) * | 2014-05-09 | 2015-11-25 | 苏毅 | Method for producing spray carbon black by using waste oil residue |
| CN104946327A (en) * | 2015-06-04 | 2015-09-30 | 成都同创伟业新能源科技有限公司 | Coal gas utilization method realized by coal-tar fraction hydro-upgrading and LNG manufacturing combination |
| RU2678278C1 (en) * | 2015-08-14 | 2019-01-24 | Орион Инджинирд Карбонз Гмбх | Methods and systems for removal of material of particles from flow of technological exhaust gases |
| CN107879311A (en) * | 2017-11-18 | 2018-04-06 | 展红明 | A kind of carbon black tail gas and coke oven tail gas combined production of ammonia alcohol synthesis gas process |
| CN113231072B (en) * | 2021-03-24 | 2022-04-26 | 西南化工研究设计院有限公司 | Catalyst for preparing isopropanol by acetone hydrogenation and application thereof |
| CN114478177A (en) * | 2022-01-21 | 2022-05-13 | 四川杰瑞恒日天然气工程有限公司 | Device and method for recovering methane in natural gas cracking carbon black tail gas and application of device and method |
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