CN103407963A - Coke oven gas hydrogen generation process - Google Patents
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- CN103407963A CN103407963A CN2013101685482A CN201310168548A CN103407963A CN 103407963 A CN103407963 A CN 103407963A CN 2013101685482 A CN2013101685482 A CN 2013101685482A CN 201310168548 A CN201310168548 A CN 201310168548A CN 103407963 A CN103407963 A CN 103407963A
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Abstract
The invention relates to a coke oven gas hydrogen generation process. The process comprises the following steps of: firstly, treating coke oven gas in a pre-purification process step and a refined naphthalene process step, and then feeding the coke oven gas into a PSA-1 system mainly comprising 12 adsorption towers for removing most of carbon dioxide in an adsorption manner; then delivering the coke oven gas into a PSA-2 system mainly comprising 10 adsorption towers for remove most of methane gas in an adsorption manner, then increasing the pressure of the obtained hydrogen-rich gas to 2.6MPa, and deoxidizing and cooling in a deoxidation system by using the compression heat of the gas; and finally, and finally carrying out hydrogen purification in a system to obtain product hydrogen. According to the coke oven gas hydrogen generation process, the coke oven gas is subjected to mature processes including PSA hydrogen extraction, methane steam conversion, transformation and the like which are scientifically combined together, 40110Nm<3>/h of hydrogen of which the purity is 99.9% can be generated from 50000Nm<3>/h of the coke oven gas, the yield rate is high, 22508Nm<3>/h of a mixed desorption gas of which the caloric value is 4276-4636kcal/Nm<3> is generated secondarily and returned to a coking unit, and the demand on coke fuel is met. According to the coke oven gas hydrogen generation process, the hydrogen output is doubled, the waste gas discharge is reduced, and the process adjustment is flexible.
Description
Technical field
The present invention relates to chemical production technical field, particularly relate to a kind of hydrogen production from coke oven gas technique.
Background technology
At present, China's traditional technology coker coal tar output has surpassed 2,200 ten thousand tons, especially in the central and west regions, Inner Mongol and Shanxi, In Shanxi Area.And coal tar processing industry general design working ability adds and building and estimating ten thousand tons of production capacity 250-300 1,495 ten thousand tons of left and right, aggregated capacity estimates that working ability is 17,000,000 tons of left and right.Due to domestic and international economic depression and the traditional technology energy consumption is high, pollute the reasons such as large, project in construction actual working rate of deep processing in 2011 of country's reply is in 60% left and right, and inferior production capacity actual consumption coal tar is about 926.9 ten thousand tons; Account for 52.97% of total coal tar ultimate production.
Therefore, coal tar hydrogenating lighting extensive market, be the development trend of Chemical Industry chain, is suitable for promoting in coal chemical industry enterprises, realizes coal resources comprehensive utilization and retrofit, the output high value-added product.
The hydrogenation of tar device needs amounts of hydrogen large (500,000 tons/a coal tar hydrogenating unit needs amounts of hydrogen 40000 Nm3/h).In prior art, the source of hydrogen is mainly by following several: 1. the methyl alcohol of take adopts steam reforming or is that raw material adopts ammonia cracking production hydrogen with liquefied ammonia as raw material, but these two kinds of method production run costs are higher, are unwell to large-scale device for producing hydrogen.2. adopt electrolytic process hydrogen manufacturing, this technique power consumption is large, production cost is high, just less in hydrogen usage, purity requirement is high, the enterprise's (as rare metal manufacture) that produces high value added product is used, the chemical industry that therefore consumes in a large number hydrogen for needs is unaccommodated.3. take the coal gasification process hydrogen manufacturing as raw material of coal or coke, the method is mostly for the production process of industrial chemicals (methyl alcohol, synthetic ammonia), the example of the hydrogen manufacturing of being directly used in was also arranged in recent years, but because of the investment (pressurized gasification such as GE, shell etc.) of hydrogen production from coal gasification larger, and long flow path, " three wastes " are processed complicated, therefore generally do not adopt to take coal or the coke water-gas method hydrogen making as raw material.
Coke-oven gas, claim again coke(oven)gas, because combustiblecomponents is many, belongs to high heating value gas, raw gas or raw gas.Refer to several bituminous coal and be mixed with coking coal, in pit kiln after high temperature carbonization, a kind of inflammable gas produced in output coke and tar products, be the byproduct of coking industry.Coke(oven)gas is mixture, its productive rate with form because of coking coal quality to some extent difference different from the coking condition, but general dry coal commercial coke oven gas per ton 300 ~ 350m3(standard state).Its main component is hydrogen (55% ~ 60%) and methane (23% ~ 27%), also contains in addition a small amount of carbon monoxide (5% ~ 8%), the above unsaturated hydrocarbons of C2 (2% ~ 4%), carbonic acid gas (1.5% ~ 3%), oxygen (0.3% ~ 0.8%)), nitrogen (3% ~ 7%).Wherein hydrogen, methane, carbon monoxide, the above unsaturated hydrocarbons of C2 are combustibleconstituents, and carbonic acid gas, nitrogen, oxygen are non-combustible component.
Therefore coke-oven plant takes full advantage of its process advantage, and the employing coke-oven gas is raw material, after purifying, transforming, then extracts to greatest extent hydrogen, is reasonable, the practicable hydrogen producing technology of current less expensive.
Traditional hydrogen production from coke oven gas technique be take 1,000,000 tons/a coker and is example: coal resource is 50000 Nm
3/ h, wherein about 25000 Nm
3/ h, can Redundant Coke-oven Gas 25000 Nm as loop fuel
3/ h is only 15000 Nm through the production by pressure swing adsorption amounts of hydrogen
3/ h, and a large amount of waste gas emptying, contaminate environment are arranged.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, provide a kind of hydrogen in coke-oven gas is produced to greatest extent, realize simultaneously the waste gas recycling, reduce exhaust gas emission, effectively reduce the hydrogen production from coke oven gas technique of environmental pollution.
The technical scheme of taking for achieving the above object is:
A kind of hydrogen production from coke oven gas technique, it is characterized in that its processing step is: after at first coke-oven gas being carried out to the de-naphthalene operation processing of the processing of preliminary cleaning operation and essence, in being sent to the PSA-1 system that mainly contains 12 adsorption towers formations, most of carbonic acid gas is sloughed in absorption, and then be sent in the PSA-2 system that mainly contains 10 adsorption towers formations, most of methane gas is sloughed in absorption, afterwards resulting hydrogen rich gas is pressurized to 2.6MPa, utilize the heat of compression of its gas in deoxygenation system, to carry out deoxidation and cooling, finally send in system and carry out obtaining product hydrogen after hydrogen purification.
Above-mentioned preliminary cleaning operation is processed and is referred to coke-oven gas to be entered when 40 ℃ of the temperature mainly contain in the preliminary cleaning system that 5 thick de-naphthalene devices form and deviate from wherein tar, naphthalene, the H of the overwhelming majority
2S, NH
3And HCN.
The de-naphthalene operation of above-mentioned essence is processed and is referred to the coke-oven gas after preliminary cleaning at pressure 0.80MPa, under ℃ condition of temperature≤40, send in the de-naphthalene system of essence that mainly contains the de-naphthalene device formation of 4 essences and further remove alkane, aromatic hydrocarbons, sulfide, nitride, ammonia and tar wherein, obtain gaseous constituent and require as tar≤0.5mg/m, naphthalene≤0.98mg/m, benzene≤1675.8mg/m, H
2S≤5.94mg/m, COS≤178.2mg/m, NH
3≤ 40.1mg/m) purified gas.
Above-mentioned purified gas after preliminary cleaning operation and the de-naphthalene operation processing of essence, at pressure 0.80MPa, is sent in the PSA-1 system under ℃ condition of temperature≤40.
Above-mentioned decarbonation gas after processing in the PSA-1 system, at pressure 0.70MPa, enters in the PSA-2 system under ℃ condition of temperature≤40.
Above-mentionedly through the resulting hydrogen rich gas of PSA-2 system, at first send into half gas product surge tank and carry out voltage stabilizing, whether determine that according to mixed stripping gas calorific value situation through the variable valve shunting, the part hydrogen rich gas enters mixed stripping gas system, residual gas goes supercharging.
Above-mentioned decarburization desorb pneumatic transmission coking return combustion utilization of sloughing through the PSA-1 system.
Above-mentionedly through methane rich stripping gas that the PSA-2 system is sloughed, enter the concentrated gas compressor under temperature≤40 ℃, the about 20kPa condition of pressure, be compressed to 3.2MPa, then be sent in conversion, change system methane conversion is become to hydrogen, and then carbon monoxide is varied to carbonic acid gas, gas after conversion through the variable valve voltage stabilizing to 2.6MPa, under ℃ condition of temperature≤40 with deoxidation after purified gas enter in the lump that hydrogen feedstock gas blend tank mixes, voltage stabilizing.
The present invention carries the coke-oven gas of coker by-product the craft science of the maturations such as hydrogen, steam methane conversion, conversion and reasonably combines through PSA, can be from 50000 Nm
3Output 40110 Nm in the coke-oven gas of/h
3/ h purity is 99.9% hydrogen, and output capacity is high, and it is 4276～4636kcal/Nm that the while by-product goes out calorific value
3Mixing stripping gas 22508 Nm
3/ h returns to coker, meets the user demand of coke oven fuel.
Hydrogen production from coke oven gas technique of the present invention has realized that hydrogen output is double, has reduced exhaust gas emission, and process adjustments is flexible.
Adopt the hydrogen that explained hereafter of the present invention goes out to produce for the coal tar hydrogenating lighting, the main products of producing: 1# lightweight coal tar (C
5～180 ℃) sulphur, nitrogen, olefin(e) centent and other impurity all very low; 180 ℃, 2# lightweight coal tar (>) good security, sulphur content are low, can be used as the high quality chemical product, also can be used as environment-friendly type fuel and use; Coal-tar pitch dispatches from the factory as the pitch blend component or is in harmonious proportion this technique of heavy fuel oil (HFO) fully can the large-scale industrialization popularization.
The accompanying drawing explanation
Fig. 1 is the process flow sheet of hydrogen production from coke oven gas technique of the present invention.
Embodiment
1, adopt the efficient coal tar metallization processes of Second Design Institute of Chemical Industry, make the coal tar time short, gas production rate is large, many 1.5 times than traditional technology, the gas of output.
2, hydrogen production from coke oven gas technique:
(1) preliminary cleaning operation: coke-oven gas enters the preliminary cleaning operation when 40 ℃ of temperature, and this operation is by the de-naphthalene device of 5 essences, the compositions such as 1 electric heater and a series of manual valves.
Utilize coke to have stronger adsorptivity, entering the thick de-naphthalene device system be comprised of 5 thick de-naphthalene devices processes, the gas bottom in and top out, the Impurity deposition of deviating from drench to be got rid of by leading in bottom, and adsorb saturated sorbent material, to adopt temperature be that the superheated vapour of 400 ℃ of left and right, pressure 0.2MPa heats and regenerates the de-naphthalene device of de-oiling.After the preliminary cleaning system, deviate from tar, naphthalene, the H of the overwhelming majority in coke-oven gas
2S, NH
3, the impurity such as HCN, obtain the less purified gas of impurity.
(2) the de-naphthalene operation of essence: the purified gas after preliminary cleaning is at pressure 0.80MPa, under ℃ condition of temperature≤40, by essence, take off the naphthalene work again, further remove wherein alkane, aromatic hydrocarbons, sulfide, nitride, ammonia, tar etc., obtain meeting the purified gas of pressure-variable adsorption unstripped gas requirement.
This operation is by 3 coke oven gas compressors (combining compression), 4 de-naphthalene devices of essences, 2 oil eliminators, 1 stripping gas well heater, 1 stripping gas water cooler and the compositions such as a series of manual valve and sequencing valve.Utilize coke to have stronger adsorptivity, purified gas enters the de-naphthalene device system of essence be comprised of the de-naphthalene device of 4 essences and processes after the one-level compression, the gas bottom in and top out, the Impurity deposition of deviating from is got rid of by leading to drench in bottom, again compressed machine secondary, by oil eliminator, remove the oil that compressor sees in after being pressurized to 0.80MPa, by this operation, further remove wherein naphthalene, alkane, aromatic hydrocarbons etc., obtain meeting the requirement of pressure-variable adsorption unstripped gas, this gaseous constituent requires as tar≤0.5mg/m, naphthalene≤0.98mg/m, benzene≤1675.8mg/m, H
2S≤5.94mg/m, COS≤178.2mg/m, NH
3≤ 40.1mg/m) purified gas.
(3) PSA-1 (PSA-CO
2/ R) decarbonation operation: the coke-oven gas after purifying treatment, at pressure 0.80MPa, under ℃ condition of temperature≤40, to send in the PSA-1 system, the process sorbent material is by most of CO2 removal, decarburization desorb pneumatic transmission coking return combustion utilizes, concentrated pneumatic transmission PSA-2 (PSA-CH
4) operation.
The PSA-1 system is comprised of 12 adsorption towers and a series of sequencing valve, the feature that this system changes with the variation of pressure the loading capacity of the difference of the aspects such as gas with various adsorptive capacity, rate of adsorption, adsorptive power and sorbent material by sorbent material, under pressurized conditions, complete the adsorption separation process of mixed gas, the gaseous fraction that depressurization desorption adsorbs, thereby realize the separation of gas, as follows by the gaseous fraction after the PSA-1 decarburization: hydrogen is 62.425%, CO
2Be 0.201%, CO is 8.453%, methane is 25.6281%, nitrogen is 1.485%, oxygen is 0.562%.
Above-mentioned adsorption tower upper strata sorbent material model is the CAN-324(silica type, main component is Si, Na, Sichuan Tianyi Science & Technology Co., Ltd), lower floor's sorbent material model is the CAN-421(alumina type K, producer:, main component is Al, producer:, adopt the 12-5-3/V flow process Sichuan Tianyi Science & Technology Co., Ltd), arbitrary moment always has 5 adsorbers to be in adsorption step, by inlet end, pass into raw material, obtain purified gas at exit end.Every adsorption tower experiences absorption (A) successively at different time, and (EiD) falls in the multistage pressure equilibrium, inverse put (D), find time (V), and balanced rise (EiR) of multistage pressure, (FR) finally boosts.It is all that pressure equalization liter for other adsorber is fully to reclaim the purified gas that will be reproduced adsorber that all pressure equalizatioies of adsorber are fallen.The inverse put step has been discharged most of impurity composition of occlusion in the adsorber, and remaining impurity is by vacuumizing the further desorb of step.Sorbent material was approximately changed once in 3 years.
(4) PSA-2 (PSA-CH
4) the demethanizing operation: will slough the concentrated gas of carbonic acid gas at pressure 0.70MPa, enter the PSA-2 system under ℃ condition of temperature≤40, in the PSA-2 system, through sorbent material, most of stripping gas (high methane gas) be removed.Hydrogen rich gas enters half gas product surge tank and carries out voltage stabilizing, according to mixed stripping gas calorific value situation, determine whether through variable valve, shunt, the part hydrogen rich gas enters mixed stripping gas system, remaining gas to the 2.6MPa left and right, utilizes the heat of compression of its gas in deoxygenation system, to carry out deoxidation and cooling through the associating compressor boost.In deoxygenator, micro amount of oxygen is under the palladium catalyst effect, and hydrogen reaction generation water, thereby reaches the effect that removes trace oxygen, and its reaction equation is as follows:
2H
2+O
2→H
2O(g)+484（KJ/mol）
Above-mentioned PSA-2 system is comprised of 10 adsorption towers and a series of sequencing valve, the feature that it changes with the variation of pressure the loading capacity of the difference of the aspects such as gas with various adsorptive capacity, rate of adsorption, adsorptive power and sorbent material by sorbent material, under pressurized conditions, complete the adsorption separation process of mixed gas, the gaseous fraction that depressurization desorption adsorbs, thus realize the separation of gas.As follows by the hydrogen rich gas gaseous fraction after this operation: hydrogen is 86.83%, CO
2Be 0.023%, CO is 4.572%, methane is 5.941%, nitrogen is 2.023%, oxygen is 0.608%.
Above-mentioned adsorption tower upper strata sorbent material model is CAN-210(gac class, main component is C, Ca, K, Na, producer: Sichuan Tianyi Science & Technology Co., Ltd), lower floor's sorbent material model is the CAN-421(alumina type, main component is Al, producer: Sichuan Tianyi Science & Technology Co., Ltd), adopt the 10-2-5/P flow process, arbitrary moment always has 3 adsorbers to be in adsorption step, by inlet end, pass into raw material, at exit end, obtain purified gas, every adsorber experiences absorption (A) successively at different time, (EiD) falls in the multistage pressure equilibrium, reverse bleeding off pressure (D), vacuumize (V), balanced rise (EiR) and finally boost (FR) of multistage pressure, it is all that pressure equalization liter for other adsorber is fully to reclaim the purified gas that will be reproduced adsorber that all pressure equalizatioies of adsorber are fallen.The inverse put step has been discharged most of impurity composition of occlusion in the adsorber, and remaining impurity is by the further desorb of evacuation step.
The intrasystem stripping gas of PSA-2 (high methane gas) is through variable valve shunting～10200Nm
3The flow of/h enters one section conversion, transformation system, in its system, carry out purification, compression, conversion and the steam reforming of methane gas, be specially: from the about 20KPa of concentrated methane gas pressure of PSA, under ℃ condition of temperature≤40, enter the concentrated gas compressor, be compressed to～3.2MP (G), after concentrated gas outlet surge tank buffering, be sent to purify after conversion procedure is preheating to the temperature that smart desulfurization needs and send smart desulfurization process.At first concentrated gas after pretreatment process is processed and pressurizeed, heats up enters can in parallel or pre-hydrogenation tank AB that use separately by two, main that hydrogenation of unsaturated hydrocarbons in concentrated gas is saturated, and the oxygen in the hydrogenation and removing concentrated gas, also there is a small amount of organic desulfurization (mercaptan, thiophene, thioether, dithiocarbonic anhydride etc.) hydrocracking to become inorganic sulfur (H
2S).From pre-hydrogenation tank AB pre-hydrogenation concentrated gas out, enter hydrogenation tank I, the organic desulfurization in concentrated gas (mercaptan, thiophene, thioether, dithiocarbonic anhydride etc.) is further transformed.Concentrated gas after the two-stage hydrocracking enter by two can go here and there can and or the thick digester AB that uses separately, remove the H generated after hydrocracking in concentrated gas
2S.For guaranteeing the requirement of technique to total sulfur in concentrated gas, a hydrogenation tank II and two smart digesters after above-mentioned technical process, have been increased.When the hydrocracking desulfurization of front can meet technique to the requiring of total sulfur, purify concentrated gas and be delivered to subsequent processing from bypass (and without rear one-level hydrocracking desulphurization system); When the hydrocracking desulfurization of front can't meet technique to the requiring of total sulfur, concentrated gas was delivered to subsequent processing through one-level hydrocracking desulphurization system later after processing, thereby by H in concentrated gas
2S is removed to below 0.1ppm.Concentrated gas after purification, preheating first passes through the shift converter I, and the CO in concentrated gas is become to CO
2, with the water vapor from the waste heat boiler drum, mix by certain steam/hydrocarbons ratio, then send first group of coil pipe of converter convection zone to be preheated to the converter entrance temperature required, then from top, enter converter and carry out steam reforming reaction.Converter is divided into radiation section and convection zone two portions.At radiation section, unstripped gas carries out conversion reaction in conversion tube, and the fuel gas burning gas also flows with process gas from top to bottom.On radiation section top, the interior gas temperature of conversion tube is low, caloric receptivity large (reactant concn is high, and conversion reaction is violent), and burning gas temperature is high; And in the radiation section bottom, gas is raise gradually along with heating gradually its temperature in conversion tube, caloric receptivity also reduces (reactant concn reduces, reacting weight little) gradually.So both effectively utilize the heating surface (heat-transfer intensity is high) of conversion tube, can control again the conversion tube pipe surface temperature unlikely too high.The convection zone of converter is the waste heat recovery section.The stack gas heating parts of organizing material in heat exchange coil that converter leaves radiation section more.The stack gas along continuous straight runs flows, and heat exchange coil is according to adding heat request and heat transfer characteristic Rational Arrangement in certain sequence.Heat exchange coil has: cold mixture heater, concentrated gas preheater, vapour generator, air preheater.Stack gas temperature after many group coil heat exchanges is down to 150 ℃ of left and right, send chimney emptying through induced draft fan.Vapour generator is the drum formula,, by the poor vapour generator that enters of severe, is heated the rear section vaporization and returns to drum through upcast from the water of water vapor drum.From converter reforming gas out, enter reforming gas waste-heat boiler.Pipe light wall pipe plank frame centered by reforming gas waste-heat boiler, tube side is made in conversion leave with rage, feedwater is heated vaporization at shell side, after gas-vapor mix is sent by useless pot upcast in the useless pot drum that is arranged in higher platform and is carried out the carbonated drink separation, water vapor send converter to use as process steam, and unnecessary water vapor send out-of-bounds steam pipe system through metering; Water leans on and the poor reforming gas waste-heat boiler that enters of the severe of upcast through useless pot downtake, so iterative cycles.Make up water through preheating adds from drum.Steam in (two drums all produce middle pressure steam) drum is mainly for conversion, deoxygenation, device companion warm.Unnecessary steam send steam user outside battery limit (BL).From the reforming gas of reforming gas waste-heat boiler, enter Middling Temp Shift Converter and carry out transformationreation, conversion gas enters the medium pressure boiler feedwater heating apparatus again and carries out heat exchange, therefrom press boiler water-suppling heater conversion gas out further to reclaim heat through the de-salted water preheater, after air cooler water cooler cooling condensation, gas-water separation, send pressure-variable adsorption separating-purifying hydrogen operation.
Conversion unstripped gas after preheating mixes with water vapour, in converting furnace, carries out following principal reaction under the effect of metalNicatalyst:
Steam reforming reaction: CH4+H2O==CO+3H2-206.4 kJ/mol
Transformationreation: CO+H2O==CO2+H2+41.2 kJ/mol
This technique has all adopted transformationreation before conversion and after transforming, but its objective is different:
One, CO is namely starting to have scission reaction more than 400 ℃, CO+H2==C+H2O, and form carbon ratio by CO, by the speed of methanogenesis carbon, want fast 3 ~ 10 times under similarity condition.In concentrated gas CO content be about ~ 15%, for avoiding the CO excessive concentration to form carbon, the conversion catalyst carbon distribution is lost activity, therefore before conversion reaction, first increase transformationreation, make CO concentration be down to about 1%(butt) left and right.
Two, the purpose of conversion is that the CO transformed in exit gas is converted into to H2, with the hydrogen output that improves the unit raw material, the cost that reduces hydrogen.
(5) PSA-3 (PSA-H
2) the purifying hydrogen of hydrogen operation
Gas after conversion and the hydrogen rich gas after deoxidation are sent to (pressure-variable adsorption separating-purifying hydrogen) PSA-3 (PSA-H
2) operation.Above-mentioned PSA-3 is comprised of 10 adsorption towers and a series of sequencing valve, the feature loading capacity of the difference of the aspects such as gas with various adsorptive capacity, rate of adsorption, adsorptive power and sorbent material changed with the variation of pressure by sorbent material, under pressurized conditions, complete the adsorption separation process of mixed gas, the gaseous fraction that depressurization desorption adsorbs, thereby realize the purification of hydrogen, the hydrogen obtained is sent into hydrogenation of tar workshop section after the variable valve voltage stabilizing.By hydrogen purity>=99.9% in gas composition after this system, CO+CO
2≤ 20ppm, O
2≤ 10ppm, ∑ S≤1ppm, pressure>=2.5MPa, temperature≤40 ℃.
Above-mentioned adsorption tower the superiors sorbent material model is the CAN-193B(molecular sieve, main component is SG, Al, Ca, Na, producer: Sichuan Tianyi Science & Technology Co., Ltd), second layer sorbent material model is CAN-210(gac class, main component is C, Ca, K, Na, producer: Sichuan Tianyi Science & Technology Co., Ltd), the 3rd layer of sorbent material model is the extraordinary sorbent material of CAN-656(, main component is CU, C, Ca, K, producer: Sichuan Tianyi Science & Technology Co., Ltd), orlop sorbent material model is the CAN-421(alumina type, main component is Al, producer: Sichuan Tianyi Science & Technology Co., Ltd), adopt the 10-2-5/P flow process, arbitrary moment always has 2 adsorbers to be in adsorption step, by inlet end, pass into raw material, at exit end, obtain gas product, every adsorber experiences absorption (A) successively at different time, (EiD) falls in the multistage pressure equilibrium, along putting (PP), reverse bleeding off pressure (D), rinse (P), balanced rise (EiR) and finally boost (FR) of multistage pressure, it is all that pressure equalization liter for other adsorber is fully to reclaim the gas product that will be reproduced adsorber that all pressure equalizatioies of adsorber are fallen.The inverse put step has been discharged most of impurity composition of occlusion in the adsorber, and remaining impurity is by the further desorb of rinse step.Adjusting is from the methane stripping gas of PSA-2 system, along venting (regulating the calorific value in stripping gas) and mixed from the stripping gas of PSA-1 system and PSA-3 system, the mixed stripping gas of approximately～6500Nm3/h flow is sent as the fuel gas of steam reforming system, remaining mixed stripping gas is sent into follow-up workshop section, (flow 22000～24000Nm3/h, calorific value be 4200 Kcal/Nm approximately to reach the required stripping gas of follow-up workshop section
3) requirement, product hydrogen is sent into hydrogenation of tar workshop section after the variable valve voltage stabilizing.
3, the coal tar of this device by-product is processed and the liquefied gas recovery system through pre-treatment, hydrogenation reaction, hydrogen make, fractional distillation, residual neat recovering system, amine.Obtain the petrol and diesel oil that cetane value is greater than 43.This device liquid yield is 74%.
Claims (8)
1. hydrogen production from coke oven gas technique, it is characterized in that its processing step is: after at first coke-oven gas being carried out to the de-naphthalene operation processing of the processing of preliminary cleaning operation and essence, in being sent to the PSA-1 system that mainly contains 12 adsorption towers formations, most of carbonic acid gas is sloughed in absorption, and then be sent in the PSA-2 system that mainly contains 10 adsorption towers formations, most of methane gas is sloughed in absorption, afterwards resulting hydrogen rich gas is pressurized to 2.6MPa, utilize the heat of compression of its gas in deoxygenation system, to carry out deoxidation and cooling, finally send in system and carry out obtaining product hydrogen after hydrogen purification.
2. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that above-mentioned preliminary cleaning operation is processed to refer to coke-oven gas to be entered when 40 ℃ of the temperature mainly contain in the preliminary cleaning system that 5 thick de-naphthalene devices form and deviate from wherein tar, naphthalene, the H of the overwhelming majority
2S, NH
3And HCN.
3. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that the de-naphthalene operation processing of above-mentioned essence refers to the coke-oven gas after preliminary cleaning at pressure 0.80MPa, under ℃ condition of temperature≤40, send in the de-naphthalene system of essence that mainly contains the de-naphthalene device formation of 4 essences and further remove alkane, aromatic hydrocarbons, sulfide, nitride, ammonia and tar wherein, obtain gaseous constituent and require as tar≤0.5mg/m, naphthalene≤0.98mg/m, benzene≤1675.8mg/m, H
2S≤5.94mg/m, COS≤178.2mg/m, NH
3≤ 40.1mg/m) purified gas.
4. according to the described hydrogen production from coke oven gas technique of claim 1 or 3, it is characterized in that above-mentioned purified gas after preliminary cleaning operation and the de-naphthalene operation of essence are processed, at pressure 0.80MPa, sends in the PSA-1 system under ℃ condition of temperature≤40.
5. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that above-mentioned decarbonation gas after processing in the PSA-1 system, at pressure 0.70MPa, enters in the PSA-2 system under ℃ condition of temperature≤40.
6. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that above-mentionedly through the resulting hydrogen rich gas of PSA-2 system, at first sending into half gas product surge tank and carrying out voltage stabilizing, according to mixed stripping gas calorific value situation, determine whether through variable valve, shunt, the part hydrogen rich gas enters mixed stripping gas system, and residual gas goes supercharging.
7. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that: above-mentioned decarburization desorb pneumatic transmission coking return combustion utilization of sloughing through the PSA-1 system.
8. according to hydrogen production from coke oven gas technique claimed in claim 1, it is characterized in that: above-mentionedly through methane rich stripping gas that the PSA-2 system is sloughed, enter the concentrated gas compressor under temperature≤40 ℃, the about 20kPa condition of pressure, be compressed to 3.2MPa, then be sent in conversion, change system methane conversion is become to hydrogen, and then carbon monoxide is varied to carbonic acid gas, gas after conversion through the variable valve voltage stabilizing to 2.6MPa, under ℃ condition of temperature≤40 with deoxidation after purified gas enter in the lump that hydrogen feedstock gas blend tank mixes, voltage stabilizing.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512702A (en) * | 2017-09-07 | 2017-12-26 | 成都巨涛油气工程有限公司 | Hydrogen production from coke oven gas technique |
| CN109795986A (en) * | 2019-01-03 | 2019-05-24 | 青海盐湖工业股份有限公司 | A kind of coke-stove gas recycling system |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN110615403A (en) * | 2019-09-30 | 2019-12-27 | 盛卫东 | Method for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
| CN111303925A (en) * | 2020-03-30 | 2020-06-19 | 陕西东鑫垣化工有限责任公司 | Method for producing hydrogen and desorbing gas to replace recycled coal gas in semi-coke process and fuel system |
| CN111320528A (en) * | 2020-03-24 | 2020-06-23 | 北京石油化工工程有限公司 | Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas |
| CN111732975A (en) * | 2020-05-19 | 2020-10-02 | 福州大学 | Blast furnace gas partial deoxidation and desulfurization method and system |
| CN112408322A (en) * | 2020-11-25 | 2021-02-26 | 西南化工研究设计院有限公司 | System and method for preparing ethanol and ethylene glycol synthesis gas through coke oven gas carbon supplementing conversion |
| CN113295504A (en) * | 2021-05-31 | 2021-08-24 | 马鞍山钢铁股份有限公司 | Composition method on-line monitoring system for metallurgical byproduct gas |
| CN113968572A (en) * | 2021-10-21 | 2022-01-25 | 福州大学 | Blast furnace and converter gas mixed gas deoxidation hydrogen production system and process |
| CN115231519B (en) * | 2022-08-09 | 2023-09-26 | 上海富禧友好能源科技有限公司 | Environment-friendly blast furnace gas hydrogen production process |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107512702A (en) * | 2017-09-07 | 2017-12-26 | 成都巨涛油气工程有限公司 | Hydrogen production from coke oven gas technique |
| CN109795986A (en) * | 2019-01-03 | 2019-05-24 | 青海盐湖工业股份有限公司 | A kind of coke-stove gas recycling system |
| CN110127613A (en) * | 2019-05-20 | 2019-08-16 | 广东国能中林实业有限公司 | A kind of efficiently advanced hydrogen production from coke oven gas technique |
| CN110615403B (en) * | 2019-09-30 | 2023-02-03 | 盛卫东 | Method for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
| CN110615403A (en) * | 2019-09-30 | 2019-12-27 | 盛卫东 | Method for preparing hydrogen meeting vehicle hydrogen standard from biomass gas |
| CN111320528A (en) * | 2020-03-24 | 2020-06-23 | 北京石油化工工程有限公司 | Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas |
| CN111303925A (en) * | 2020-03-30 | 2020-06-19 | 陕西东鑫垣化工有限责任公司 | Method for producing hydrogen and desorbing gas to replace recycled coal gas in semi-coke process and fuel system |
| CN111732975A (en) * | 2020-05-19 | 2020-10-02 | 福州大学 | Blast furnace gas partial deoxidation and desulfurization method and system |
| CN112408322A (en) * | 2020-11-25 | 2021-02-26 | 西南化工研究设计院有限公司 | System and method for preparing ethanol and ethylene glycol synthesis gas through coke oven gas carbon supplementing conversion |
| CN113295504A (en) * | 2021-05-31 | 2021-08-24 | 马鞍山钢铁股份有限公司 | Composition method on-line monitoring system for metallurgical byproduct gas |
| CN113295504B (en) * | 2021-05-31 | 2023-03-03 | 马鞍山钢铁股份有限公司 | Composition method on-line monitoring system for metallurgical byproduct gas |
| CN113968572A (en) * | 2021-10-21 | 2022-01-25 | 福州大学 | Blast furnace and converter gas mixed gas deoxidation hydrogen production system and process |
| CN115231519B (en) * | 2022-08-09 | 2023-09-26 | 上海富禧友好能源科技有限公司 | Environment-friendly blast furnace gas hydrogen production process |
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