CN205347354U - Device of low temperature pyrolysis coal gas system natural gas and coproduction hydrogen - Google Patents
Device of low temperature pyrolysis coal gas system natural gas and coproduction hydrogen Download PDFInfo
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- CN205347354U CN205347354U CN201520811406.8U CN201520811406U CN205347354U CN 205347354 U CN205347354 U CN 205347354U CN 201520811406 U CN201520811406 U CN 201520811406U CN 205347354 U CN205347354 U CN 205347354U
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Abstract
The utility model provides a device of low temperature pyrolysis coal gas system natural gas and coproduction hydrogen, including low temperature pyrolysis poly -generation unit, washing purification unit, the hydrogenation unit, smart desulfurization unit, unit methanation unit and the pressure swing adsorption unit of changeing is is in advance imported and exported and is established ties in proper order, to be equipped with the low order coal preliminary treatment that the coal measures was all sent here through low temperature pyrolysis poly -generation unit, purification unit further purifies through the washing, all unsaturated hydrocarbons in with coal gas are transformed into corresponding saturated hydro carbons through the hydrogenation unit, simultaneously be transformed into H2S with the organic sulfur, reduce to <through the H2S content of smart desulfurization unit in with the feed gas, 0.1ppm, senior hydro carbons more than the C2 of technology in with low temperature pyrolysis coal gas is whole through changeing in advance is transformed into methane, has improved the utilization ratio of carbon, and coproduction hydrogen, solved methanation catalyst and in advance conversion catalyst need the demand of high -purity hydrogen in when reduction, realized that the high -efficient hierarchical of low order coal utilizes, process flow is simple, maneuverability is strong.
Description
Technical field
This utility model belongs to natural gas manufacturing technology field, particularly to the system of a kind of low temperature distillation coal gas preparing natural gas co-production hydrogen.
Background technology
The energy national conditions of China are " rich coals, oil starvation, few gas ", the ratio being consumed in primary energy consumption of coal has accounted for more than 70%, wherein the terminal occupation mode of coal is still based on traditional burning, the valuable chemicals contained in coal is caused effectively to utilize, and coal directly burns, especially burning low-order coal calorific value is all relatively low, not only waste resource, and cause serious environmental pollution, especially current environment goes from bad to worse, urgently need us to develop coal grading and utilize technology, increase the added value of coal, and improve coal calorific value, reduce pollutant emission.
Natural gas is as a kind of efficient, safe and clean fossil energy, and the ratio in global Energy Consumption rises year by year；Enhancing and the raising of quality of life along with people's environmental consciousness, particularly the increasing the weight of of China's haze weather, the demand of natural gas strengthens year by year, deeply develop the low temperature distillation co-production technology of coal, utilize the dry distillation gas that calorific value is relatively low, it is transformed into cleaning, efficient natural gas, rich producing coal tar and semi-coke simultaneously, not only achieve the comprehensive utilization of coal resources, and the clean and effective meeting coal utilizes technology path, also extenuated the phenomenon of China's petroleum resources relative shortage simultaneously, and to safeguarding Chinese energy safety, realize energy-saving row, protection environmental ecologies etc. are all significant.
In coal gas produced by the low temperature distillation of coal, methane content is less, and calorific value of gas is low, and the process costs directly purifying methane from coal gas is higher, and energy utilization rate is low, is unfavorable for that industrialization is amplified, and containing substantial amounts of H in the resolution gas after methane separation2, the precious resources such as CO and higher hydrocarbons, directly resolution gas is passed into boiler combustion, the added value that can lose coal causes the wasting of resources, and does not meet the clean utilization route of coal.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the purpose of this utility model is in that to provide the device of a kind of low temperature distillation coal gas preparing natural gas co-production hydrogen, has energy consumption low, easy to operate, realizes low-order coal clean and effective simultaneously and utilizes.
To achieve these goals, the technical solution adopted in the utility model is:
A kind of system of low temperature distillation coal gas preparing natural gas co-production hydrogen, including low temperature distillation Poly-generation unit 1, the dry distillation gas outlet of low temperature distillation Poly-generation unit 1 is connected with the gas access of water washing cleaning unit 2, the gas outlet of water washing cleaning unit 2 is connected with the gas access of hydrogenation unit 3, the gas outlet of hydrogenation unit 3 is connected with the gas access of fine de-sulfur unit 4, the gas outlet of fine de-sulfur unit 4 is connected with the gas access of pre-inversion unit 5, the gas outlet of pre-inversion unit 5 is connected with the gas access of methanation unit 6, the gas outlet of methanation unit 6 is connected with the gas access of psa unit 7；Wherein the gas of fine de-sulfur unit 4 is connected with the gas of psa unit 7 by cross-line.
A kind of method of low temperature distillation coal gas preparing natural gas co-production hydrogen, comprises the following steps:
(1), passing through to completely cut off air at 400-600 DEG C of heating, by-product semi-coke, coal tar and dry distillation gas by the low-order coal that standby coal measures system is sent here by low temperature distillation Poly-generation unit 1, wherein the component of dry distillation gas includes CH by volume4Content 28-40%, CO content 10-15%, H2Content 25-40%, CO2Content 5-10%, C2H6Content 2-8%, C2H4Content 1-4%, C3H6Content 0.5-3%, C3H8Content 0.4-2.5%, C4H8Content 0.2-2%, H2S content 2000-6000ppm and NH3Content 300-800ppm；
(2) the shower water purifying process adopted by water washing cleaning unit 2, is purified further by pretreated low temperature distillation coal gas, removes the ammonia in dry distillation gas and sulfide, to reduce the load of follow-up desulfurization process；
(3) by hydrogenation unit 3, all unsaturated hydrocarbons in coal gas are transformed into the saturated hydrocarbons of correspondence, organic sulfur are transformed into H simultaneously2S；
(4) adopt dry desulfurizing process by fine de-sulfur unit 4, utilize solid ZnO desulfurization, by the H in unstripped gas2S content is reduced to < 0.1ppm；
(5) by gas after desulfurization by pre-inversion unit 5, the steam preconversion catalyst for hydrocarbon of high nickel content is adopted, wherein NiO content 48-68%, Al in mass ratio in catalyst2O3Content 15-36%, content of MgO 1.2-4.8%, La2O3Content 1.2-4.8%, CaO content 5-12%, K2O content 0.5-1.2%, graphite 1.5-4.5%；This unit pressure 1.5-3.5MPa, temperature 400-800 DEG C and when steam/hydrocarbons ratio 2-4, make the higher hydrocarbon generation pre-inversion reaction of more than C2 in coal gas generate methane；The component that wherein coal gas after pre-inversion reaction includes has: CH4Content 30-50%, CO content 13-18%, H2Content 30-60%, CO2Content 10-15% and containing a small amount of water vapour and other foreign gas；
(6) by gas after pre-inversion by methanation unit 6, adopting the methanation catalyst of low nickel-content, wherein methanation catalyst component is NiO content 12-24%, Al in mass ratio2O3Content 32-74%, content of MgO 1.2-4.8%, La2O3Content 1.2-4.8%, CaO content 5-12%, K2O content 0.5-1.2%, content of graphite 1.5-4.5%；By methanation catalyst by the active component in unstripped gas: H2, CO and CO2There is methanation reaction so that the methane concentration of its generation can reach 75-90%；
(7) gas after methanation reaction passes into psa unit 7, is produced methane and the product LNG co-production high-purity hydrogen of high concentration by pressure swing adsorption technique；
Clean gas after fine de-sulfur is directly connected with psa unit 7 by cross-line by described fine de-sulfur unit 4 before whole system is run, produce high-purity hydrogen, the catalyst reduction being pre-inversion unit 5 and methanation unit 6 at system initial operating stage provides required hydrogen, change according to working condition simultaneously, reduce the production load of methanation unit 6.
Advantage of the present utility model:
Adopt the low temperature distillation Poly-generation technology of coal, it is achieved that the clean and effective of low-order coal utilizes, produce the compressed natural gas co-production hydrogen of high heating value；The dry distillation gas that this system produces first carried out pre-inversion reaction before methanation unit, higher hydrocarbons in dry distillation gas is completely converted into methane, achieve the efficient utilization of carbon, and effectively prevent the carbon distribution of methanation catalyst, improve the service life of catalyst, simultaneously by changing the amount of water vapour in pre reforming Process, it is possible to regulate the hydrogen-carbon ratio of downstream methanation workshop section；The hydrogen of the psa unit richness production of high purity of native system, not only solve the demand of required high-purity hydrogen during the catalyst reduction of pre-inversion and methanation, produce load by modulation methanation in process of production simultaneously, co-producing high-purity hydrogen, and utilize high-purity hydrogen the coal tar that low temperature distillation polygenerations systeme produces can carry out hydrogenation upgrading to obtain senior oil product.
Accompanying drawing explanation
Accompanying drawing is structural representation of the present utility model.
Detailed description of the invention
Below in conjunction with accompanying drawing, this utility model is described in detail.
A kind of system of low temperature distillation coal gas preparing natural gas co-production hydrogen, including low temperature distillation Poly-generation unit 1, the dry distillation gas outlet of low temperature distillation Poly-generation unit 1 is connected with the gas access of water washing cleaning unit 2, the gas outlet of water washing cleaning unit 2 is connected with the gas access of hydrogenation unit 3, the gas outlet of hydrogenation unit 3 is connected with the gas access of fine de-sulfur unit 4, the gas outlet of fine de-sulfur unit 4 is connected with the gas access of pre-inversion unit 5, the gas outlet of pre-inversion unit 5 is connected with the gas access of methanation unit 6, the gas outlet of methanation unit 6 is connected with the gas access of psa unit 7, product LNG is obtained by the methane tinning of pressure swing adsorption technique separation of high-concentration, other gas isolated can directly feed boiler combustion, or further separation joint-product high concentration hydrogen；
Described low temperature distillation Poly-generation unit 1 is to pass through to completely cut off air at 400-600 DEG C of heating, by-product semi-coke, coal tar and dry distillation gas by the low-order coal that standby coal measures system is sent here, and wherein the key component of dry distillation gas has CH4Content 28-40%, CO content 10-15%, H2Content 25-40%, CO2Content 5-10%, C2H6Content 2-8%, C2H4Content 1-4%, C3H6Content 0.5-3%, C3H8Content 0.4-2.5%, C4H8Content 0.2-2%, H2S content 2000-6000ppm and NH3Content 300-800ppm；
Described water washing cleaning unit 2 is the shower water purifying process adopted, and is mainly purified further by pretreated dry distillation gas, to remove ammonia in dry distillation gas and a small amount of sulfide, to reduce the load of follow-up desulfurization process；Sewage after its spray participates in the raw coal washing process of standby coal measures system, filtered the series of measures such as purification, phosphoric acid softening and stripper process afterwards by biochemical treatment, semi-coke and be directly used in boiler feedwater use, thus effectively preventing a large amount of discharges of sewage, improve the cyclic utilization rate of water resource；
Described hydrogenation unit 3 adopts ferrum molybdenum hydrogenation catalyst, all unsaturated hydrocarbons in coal gas is transformed into the saturated hydrocarbons of correspondence, organic sulfur is transformed into H simultaneously2S；
Described fine de-sulfur unit 4 adopts dry desulfurizing process, utilizes solid ZnO desulfurization, by the H in unstripped gas2S content is reduced to that < 0.1PPm, to ensure the operating mode that the catalyst activity that the catalyst that downstream section uses will not produce to occur reduces because of sulfur poisoning.
Described pre-inversion unit 5 adopts the steam preconversion catalyst for hydrocarbon of high nickel content, wherein NiO content 48%, Al in pre-converting catalyst2O3Content 32%, content of MgO 3.2%, La2O3Content 2.3%, CaO content 11%, K2O content 0.6%, content of graphite 2.9%；In unstripped gas, be equipped with quantitative water vapour, make the higher hydrocarbon generation pre-inversion reaction of more than C2 in coal gas generate methane, the operating conditions of its pre-inversion unit pressure 1.5-3.5MPa, temperature 400-800 DEG C, steam/hydrocarbons ratio 2-4 when；Wherein in the coal gas after pre-inversion reaction, key component has CH4Content 30-50%, CO content 13-18%, H2Content 30-60%, CO2Content 10-15% and a small amount of water vapour and other foreign gas；
Described methanation unit 6 adopts the methanation catalyst of low nickel-content, and wherein methanation catalyst component is NiO content 14%, Al2O3Content 66%, content of MgO 3.2%, La2O3Content 3.2%, CaO content 11%, K2O content 1.0%, content of graphite 1.6%；By methanation catalyst by the active component in unstripped gas such as hydrogen, carbon monoxide and carbon dioxide generation methanation reaction, the methane concentration of its generation can reach 75-90%；
Described psa unit 7 adopts methane that pressure swing adsorption technique obtains high concentration pressurized liquefied preparation to be processed into product LNG, and the residual gas after separation can be immediately directed against boiler combustion；In actual production, methanation unit 6 can be reduced according to working condition and produce load, or by cross-line, the clean gas after fine de-sulfur is directly connected with psa unit 7, produce high-purity hydrogen in a large number, in order to for the hydrogen that the catalyst reduction offer of pre-inversion unit 5 and methanation unit 6 is required.
Described fine de-sulfur unit 4 is connected with psa unit 7 before whole system is run, produce high-purity hydrogen, the catalyst reduction being pre-inversion unit 5 and methanation unit 6 at system initial operating stage provides required hydrogen, which save the energy, make pre-inversion unit 5 and methanation unit 6 outsourcing need not connect hydrogen again, change according to working condition, it is possible to reduce the production load of methanation unit 6 simultaneously.
Above-mentioned each unit is all chemical industry, the conventional use of device of different process section, and this patent is to adopt new technological design route and new technological parameter to realize low temperature distillation coal gas preparing natural gas co-production hydrogen.
A kind of method of low temperature distillation coal gas preparing natural gas co-production hydrogen, comprises the following steps:
(1), passing through to completely cut off air at 400-600 DEG C of heating, by-product semi-coke, coal tar and dry distillation gas by the low-order coal that standby coal measures system is sent here by low temperature distillation Poly-generation unit 1, wherein the component of dry distillation gas includes CH4Content 28-40%, CO content 10-15%, H2Content 25-40%, CO2Content 5-10%, C2H6Content 2-8%, C2H4Content 1-4%, C3H6Content 0.5-3%, C3H8Content 0.4-2.5%, C4H8Content 0.2-2%, H2S content 2000-6000ppm and NH3Content 300-800ppm；
(2) the shower water purifying process adopted by water washing cleaning unit 2, is purified further by pretreated low temperature distillation coal gas, removes the ammonia in dry distillation gas and sulfide, to reduce the load of follow-up desulfurization process；
(3) by hydrogenation unit 3, all unsaturated hydrocarbons in coal gas are transformed into the saturated hydrocarbons of correspondence, organic sulfur are transformed into H simultaneously2S；
(4) adopt dry desulfurizing process by fine de-sulfur unit 4, utilize solid ZnO desulfurization, by the H in unstripped gas2S content is reduced to < 0.1ppm；
(5) by gas after desulfurization by pre-inversion unit 5, the steam preconversion catalyst for hydrocarbon of high nickel content, wherein NiO content 48-68%, Al in catalyst are adopted2O3Content 15-36%, content of MgO 1.2-4.8%, La2O3Content 1.2-4.8%, CaO content 5-12%, K2O content 0.5-1.2%, graphite 1.5-4.5%；This unit pressure 1.5-3.5MPa, temperature 400-800 DEG C and when steam/hydrocarbons ratio 2-4, make the higher hydrocarbon generation pre-inversion reaction of more than C2 in coal gas generate methane；The component that wherein coal gas after pre-inversion reaction includes has: CH4Content 30-50%, CO content 13-18%, H2Content 30-60%, CO2Content 10-15% and containing a small amount of water vapour and other foreign gas；
(6) by gas after pre-inversion by methanation unit 6, adopting the methanation catalyst of low nickel-content, wherein methanation catalyst component is NiO content 12-24%, Al2O3Content 32-74%, content of MgO 1.2-4.8%, La2O3Content 1.2-4.8%, CaO content 5-12%, K2O content 0.5-1.2%, content of graphite 1.5-4.5%；By methanation catalyst by the active component in unstripped gas: H2, CO and CO2There is methanation reaction so that the methane concentration of its generation can reach 75-90%；
(7) gas after methanation reaction passes into psa unit 7, is produced methane and the product LNG co-production high-purity hydrogen of high concentration by pressure swing adsorption technique.
Claims (2)
1. the device of a low temperature distillation coal gas preparing natural gas co-production hydrogen, it is characterized in that, including low temperature distillation Poly-generation unit (1), the dry distillation gas outlet of low temperature distillation Poly-generation unit (1) is connected with the gas access of water washing cleaning unit (2), the gas outlet of water washing cleaning unit (2) is connected with the gas access of hydrogenation unit (3), the gas outlet of hydrogenation unit (3) is connected with the gas access of fine de-sulfur unit (4), the gas outlet of fine de-sulfur unit (4) is connected with the gas access of pre-inversion unit (5), the gas outlet of pre-inversion unit (5) is connected with the gas access of methanation unit (6), the gas outlet of methanation unit (6) is connected with the gas access of psa unit (7)；Wherein the gas of fine de-sulfur unit (4) is connected with the gas of psa unit (7) by cross-line.
2. the device of a kind of low temperature distillation coal gas preparing natural gas co-production hydrogen according to claim 1, it is characterized in that, clean gas after fine de-sulfur is directly connected with psa unit (7) by cross-line by described fine de-sulfur unit (4) before whole system is run, produce high-purity hydrogen, required hydrogen is provided in the catalyst reduction that system initial operating stage is pre-inversion unit (5) and methanation unit (6), change according to working condition simultaneously, reduce the production load of methanation unit (6).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255531A (en) * | 2015-10-19 | 2016-01-20 | 中国华能集团清洁能源技术研究院有限公司 | System and method for natural gas production and hydrogen co-production through low-temperature dry distillation gas |
| CN108310990A (en) * | 2018-01-31 | 2018-07-24 | 新疆宣力环保能源有限公司 | Coal tar hydrogenating dry gas desulfurization recovery technology |
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- 2015-10-19 CN CN201520811406.8U patent/CN205347354U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255531A (en) * | 2015-10-19 | 2016-01-20 | 中国华能集团清洁能源技术研究院有限公司 | System and method for natural gas production and hydrogen co-production through low-temperature dry distillation gas |
| CN105255531B (en) * | 2015-10-19 | 2018-07-06 | 中国华能集团清洁能源技术研究院有限公司 | A kind of system and method for low temperature distillation coal gas preparing natural gas parallel connection hydrogen producing |
| CN108310990A (en) * | 2018-01-31 | 2018-07-24 | 新疆宣力环保能源有限公司 | Coal tar hydrogenating dry gas desulfurization recovery technology |
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