CN104058368A - Process and system for producing hydrogen by converting hydrocarbon-containing tail gas - Google Patents
Process and system for producing hydrogen by converting hydrocarbon-containing tail gas Download PDFInfo
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- CN104058368A CN104058368A CN201410254785.5A CN201410254785A CN104058368A CN 104058368 A CN104058368 A CN 104058368A CN 201410254785 A CN201410254785 A CN 201410254785A CN 104058368 A CN104058368 A CN 104058368A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention relates to a process and a system for producing hydrogen by converting hydrocarbon-containing tail gas, and aims to solve the problems of high equipment investment, high operation cost and complicated system in an existing process for producing hydrogen by converting hydrocarbon-containing tail gas. According to the process, heat energy of high-temperature process gas of a conversion furnace is reclaimed by virtue of a waste heat boiler and a plurality of heat exchangers, and is used for preheating feed gas, supplying water to a boiler and by-producing middle-pressure saturated steam, heat in the system can be well reclaimed, consumption of a heat furnace and combustion gas can be reduced, and the process and the system have the advantages of simple process, simple control, effective system heat reclamation, energy consumption reduction and equipment investment conservation.
Description
Technical field
The present invention relates to a kind of process for making hydrogen and system, specifically a kind of hydrocarbonaceous tail gas reforming hydrogen manufacturing technique and system.
Background technology
In modern large-size chemical field, acetylene as processed in Sweet natural gas, fixed bed crushed coal pressure gasifying, all can produce a large amount of containing CH in the flow processs such as gasification synthetic oil and coke-oven gas
4in the tail gas of hydro carbons, process and fully utilize containing CH
4in the tail gas of hydro carbons, prepare hydrogen, not only realized the processing of waste gas, all significant for environment protection and device volume increase.
The explained hereafter method that the hydro carbons (Sweet natural gas etc.) of abroad take is raw material hydrogen manufacturing, mainly contain self-heating conversion method, with take the techniques such as partial oxidation process that oil, heavy oil be raw material, utilize in addition the hydrogen-rich gases such as ammonia factory off-gas, methanation tail gas, methanol-fueled exhaust, catalytic reforming tail gas to carry out the refining hydrogen that obtains certain purity of the methods such as pressure-variable adsorption, low temperature process or film permeation.In numerous process for making hydrogen routes, the Steam Reforming Process that the hydro carbons (Sweet natural gas) of take is raw material occupies larger advantage hydrogen manufacturing is industrial.
Generally in Methane Conversion, independent process furnace need to be set raw material tail gas, saturation steam etc. are carried out to preheating and overheated to by-product saturation steam, process furnace heats by fuel gas.In patent ZL200910195146.5, methanol synthesis loop needs to carry out preheating by process furnace before speeding to exit and entering converter, process furnace has adopted self-priming two sections of radiation, take first to use convection zone, the rear design with radiation section, tail gas, tail gas+steam heating are arrived to required temperature, the setting of process furnace, make device complicated, operation easier strengthens, investment raises, and has also increased fuel gas consumption and running cost, has reduced the comprehensive utilization ratio of energy.
Summary of the invention
The object of the invention is in order to solve the problems of the technologies described above, provide a kind of technique simple, control easy, efficient recovery system heat energy, reduce energy consumption, save the hydrocarbonaceous tail gas reforming hydrogen manufacturing technique of facility investment.
The present invention also provides a kind of system for above-mentioned technique.
Technique of the present invention is sent into unstripped gas after being preheated to 110-130 ℃ in feed gas heater and is delivered to after heat exchanger continues to be heated to 550～650 ℃ again and enter converter, going out reacted 950～1100 ℃ of high-temperature technology gases of converter sends in the useless pot of the conversion by-product that is connected with drum and presses saturation steam, process gas cooling is sent into after being down to 600～700 ℃ after heat exchanger and unstripped gas heat exchange successively, deliver to again after reforming gas water cooler and oiler feed heat exchange are cooled to 250～300 ℃ and send into shift converter, the variation temperature degree that goes out shift converter is 220～250 ℃, CO concentration is down to volume percent below 0.8%, described conversion gas is after feedwater preheater and feedwater heat exchange cooling, through feed gas heater and the further heat exchange of unstripped gas, be cooled to 160～190 ℃ again, then through air cooler, be cooled to 60 ℃ successively, enter 1# gas-liquid separator and carry out gas-liquid separation, the conversion gas that tank deck is drawn is cooled to 40 ℃ through water cooler and enters the further separation of 2# gas-liquid separator, the conversion pneumatic transmission that tank deck is drawn is carried hydrogen system and is done further processing, obtain high-purity hydrogen, described oiler feed is sent into reforming gas water cooler again and is preheated to 200～260 ℃ and sends into drum again after feedwater preheater and conversion gas heat exchange.
Described by drum, drawn in pressure saturation steam be divided into three strands, first strand to send vapor superheater to carry out overheated, sends into oxygen preheat device for second strand for preheating, enter the pure oxygen of converter as heating steam, sneaks in described pure oxygen for the 3rd strand as safe steam.
Described shift converter is two-part shift converter, and the temperature of one section outlet reaches 370 ℃～410 ℃ conversion gas, and through vapor superheater, to press saturation steam to carry out in to first strand overheated, then after demineralized-water preheater is cooled to 200～220 ℃, deliver to two sections of shift converters.
In first strand, press saturation steam to press superheated vapour in forming after vapor superheater is overheated, be divided into two parts, a part is sent out-of-bounds middle pressure steam pipe network, and another part mixes with unstripped gas as process steam to be delivered to converter and participate in reaction after heat exchanger preheating.
While going into operation, the unstripped gas that goes out feed gas heater is first sent into after the process furnace that goes into operation is heated to 550～650 ℃ and is sent into converter.
Hydrocarbonaceous tail gas reforming hydrogen manufacturing system of the present invention, comprise converter, the outlet of described converter is successively through with the useless pot of the conversion of drum, heat exchanger, reforming gas water cooler, shift converter, feedwater preheater, feed gas heater, air cooler, 1# gas-liquid separator, water cooler, 2# gas-liquid separator and carry hydrogen system and be connected, and the unstripped gas entrance of described converter exports and is connected with the unstripped gas of feed gas heater through heat exchanger; The water inlet of described drum is connected with the water inlet of feedwater preheater through reforming gas water cooler.
The oxygen intake of described converter is connected with the oxygen outlet of oxygen preheat device; The vapour outlet of described drum is communicated with steam-in, the steam-in of oxygen preheat device and the oxygen intake of converter of vapor superheater respectively.
Described shift converter is two-part shift converter, and one section outlet is connected with two sections of entrances through vapor superheater, demineralized-water preheater;
The vapour outlet of described vapor superheater shell-side is communicated with the unstripped gas entrance of heat exchanger shell-side and middle pressure steam pipe network out-of-bounds respectively.
The unstripped gas outlet of described feed gas heater is also connected with the unstripped gas entrance of converter through the process furnace that goes into operation.
Process system of the present invention comprises unstripped gas preheating, methane and the hydrocarbon conversion, CO conversion, recovery of heat, carries the processing steps such as hydrogen, phlegma air lift, the tail gas producing in the flow processs such as unstripped gas acetylene as processed in Sweet natural gas, fixed bed crushed coal pressure gasifying, gasification synthetic oil and coke-oven gas that are applicable to process, as contained CH
4: the gas of 10～60mol% and other hydro carbons.
Native system is that take containing methane and other hydro carbons tail gas is raw material, the catalyzed conversion that the pure oxygen of take is oxygenant, the needed high purity H of production equipment
2.This device goes out methane content in the reforming gas of battery limit (BL) and reaches below 0.6mol%, and the CO volume content after conversion gas is down to below 0.8mol%, through carrying the H after hydrogen system is processed
2content can reach 99.5mol%, has met device to high purity H
2requirement.
The present invention adopts the high temperature producing after methane conversion to carry out preheating material gas, utilize the high-temperature technology gas of converter outlet to press saturation steam in transforming useless pot recovery heat and producing, with the steam of by-product, be used as process steam, preheated oxygen etc., at gas temperature, be reduced to after 600～700 ℃ simultaneously, be used for again preheating material gas, thereby put forward high-octane comprehensive utilization ratio.With process furnace, carry out preheating gas compared to the past, the advantage that adopt the self-produced heat energy recovery of native system to have more and save facility investment, reduces energy consumption.
The native system setting process furnace bypass that goes into operation, for preheating material gas under initial start-up operating mode, guarantee to react and normally carry out, after driving successfully, close go into operation process furnace and relevant pipeline, by heat exchanger utilization, transform the thermal source producing and heat the unstripped gas of sending converter to.
Shift converter one section outlet, it is overheated that the middle pressure saturation steam of drum being drawn through vapor superheater carries out, cooled conversion gas is being delivered to two sections of shift converters again after demineralized-water preheater is cooling, both effectively utilized the reaction heat centering of a section to press saturation steam to carry out overheated, also make one section of conversion gas effective temperature-reducing out, kill two birds with one stone.
Described unstripped gas can be the tail gas producing in the flow processs such as acetylene as processed in Sweet natural gas, fixed bed crushed coal pressure gasifying, gasification synthetic oil and coke-oven gas, as contained CH
4: the gas of 10～60mol% and other hydro carbons.
Tool of the present invention has the following advantages and beneficial effect:
1) system of the present invention is not established process furnace, has saved the investment of the aspects such as apparatus body, instrument and interlocked control;
2) process system of the present invention operation is more easy, is easy to control, and has wide range of applications, and can be used for synthetic ammonia, methyl alcohol is synthetic and the methane-rich gas reforming hydrogen manufacturing process such as coal liquefaction device;
3) converter outlet high-temperature technology gas is used for preheating material gas, byproduct steam etc., has realized the comprehensive utilization of energy, energy-saving and cost-reducing; And the steam of by-product is also partly as reuses such as process steam, safe steam;
4) native system only arranges the process furnace that goes into operation, during normal operation, without consume fuel gas, although compare byproduct steam with band process furnace flow process, slightly reduce, because fuel gas cost is far above steam cost, device long-time running, cost-saved, economic profit is considerable.
5) take 1,200,000 tons/year of coal liquefaction device for producing hydrogen is example, the technical process of employing native system can reduce process furnace and relevant device investment reaches 4000～5,000 ten thousand Renminbi, reduce fuel gas simultaneously and consume about 4700Nm3/h (2300kJ/kmol), compare annual consumption minimizing with process furnace flow process and amount to Renminbi～7,000,000.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention and system diagram.
In figure, (1) stripping tower, (2) oxygen preheat device, (3) converter, (4) transform useless pot, (5) drum, (6) process furnace that goes into operation, (7) heat exchanger, (8) reforming gas water cooler, (9) shift converter, (9.1) one sections, (9.2) two sections, (10) vapor superheater, (11) demineralized-water preheater, (12) feedwater preheater, (13) feed gas heater, (14) air cooler, (15) 1# gas-liquid separator, (16) water cooler, (17) 2# gas-liquid separator, (18) condensate pump, (19) carry hydrogen system, (20) phlegma preheater.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail:
System embodiment:
The outlet of described converter 3 is connected with one section of 9.1 entrance of shift converter 9 through being connected with pipe side, the pipe side of heat exchanger 7, the pipe side of reforming gas water cooler 8 of the useless pot 4 of conversion of drum 5 successively, and a section 9.1 of described shift converter 9 exports successively through the pipe side of vapor superheater 10, the pipe side of demineralized-water preheater 11 is connected with two section of 9.2 entrance of shift converter 9.Two section 9.2 of described shift converter 9 outlet successively through the pipe side of feedwater preheater, the pipe side of feed gas heater, air cooler, 1# gas-liquid separator, water cooler, 2# gas-liquid separator with carry hydrogen system and be connected, the unstripped gas entrance of described converter 3 exports and is connected through the shell-side of heat exchanger 7 and the unstripped gas of feed gas heater 13 shell-sides; The oxygen intake of described converter 3 is connected with the oxygen outlet of oxygen preheat device 2 shell-sides.
The vapour outlet of described drum 5 is connected with the steam-in of described vapor superheater 10 shell-sides respectively, the steam-ins of side managed by oxygen preheat device 2 and the oxygen intake of converter 3 is communicated with.The water inlet of described drum 5 is connected with the water inlet of feedwater preheater 12 shell-sides through the shell-side of reforming gas water cooler 8.The vapour outlet of described vapor superheater 10 shell-sides is communicated with the unstripped gas entrance of heat exchanger 7 shell-sides and middle pressure steam pipe network out-of-bounds respectively.The unstripped gas outlet of described feed gas heater 13 shell-sides is also connected with the unstripped gas entrance of converter 3 through the process furnace 6 that goes into operation.
The useless pot 4 of described conversion can adopt fixed tube sheet type, and high temperature side is designed to manage side, and pipe side need be carried out heat protection, and shell-side medium is oiler feed.
Heat exchanger 7 can be selected U-shaped tube heat-exchanger structural shape, can solve preferably the stress problem of the thermal expansion producing between the heat transfer tube of high temperature in heat exchange equipment and housing, makes equipment design safety reliable.
Technical process is described as follows.
The unstripped gas established technology device exhaust that battery limit (BL) comes (SG, 5.0～5.5MPaG, 40～70 ℃), CH
4content is 10～60mol%, other hydro carbons < 10mol%, through feed gas heater 13, be preheated to after 110～130 ℃ with a part of superheated vapour from vapor superheater 10 (5.2～5.6MPaG, 340 ℃～360 ℃) and mix, the gas mixture of tail gas+steam is sent to heat exchanger 7 by high-temperature technology gas heating to 550～650 ℃ from converter 3, then delivers to the unstripped gas entrance of converter 3.
Pure oxygen (O from air separation facility
26.0～6.5MPaG, 10 ℃～normal temperature) through oxygen preheat device 2 and middle pressure saturation steam heat exchange from drum 5, pure oxygen is preheating to 180～240 ℃, then a small amount of equally from the middle pressure saturation steam of the safe steam of conduct of drum 5 to filling in the pure oxygen after preheating, through the oxygen intake of converter 3, send into converter and react generation heat of high temperature with tail gas, by from thermal transition and under catalyst action, react and generate H
2, the high temperature process gas (950～1100 ℃) such as CO.Converter 3 pure oxygen burners can adopt circulating water.
The high-temperature technology gas that goes out converter is introduced into the pipe side recovery heat that transforms useless pot 4, utilize and in drum 4 by-products, press saturation steam (5.2～5.6MPaG, 267～272 ℃), the process gas temperature that goes out to transform useless pot 4 is down to 600～700 ℃ by 950～1100 ℃, after through the pipe side of over-heat-exchanger 7 and the tail gas heat exchange of shell-side, be cooled to 295 ℃～345 ℃ successively, pipe side and shell-side boiler through reforming gas water cooler 8 is cooled to 250～300 ℃ to heat exchange again, through the process gas (CH of recovery of heat
4be down to 0.3% volume percent) send into 9 one sections of shift converters, the conversion gas temperature of one section of 9.1 outlet of shift converter reaches 370 ℃～410 ℃, it is overheated that one section of conversion gas presses saturation steam to carry out through the pipe side of vapor superheater 10 in to the part from drum 5, steam after overheated (MS) part is mixed with the tail gas of sending into the unstripped gas entrance of heat exchanger 7 shell-sides as process steam, and another part is delivered to middle pressure steam pipe network out-of-bounds.Through the cooled one section of conversion gas of vapor superheater 10 heat exchange, after demineralized-water preheater 11 is further cooling, deliver to 9 two sections of shift converters again.
220～250 ℃ of shift converter 9 second stage exit conversion gas temperature, CO concentration is down to volume percent below 0.8%, go out the conversion gas of 9 two sections of shift converters, through the pipe side of feedwater preheater 12 and the oiler feed heat exchange of shell-side, reclaim heat, through the pipe side of feed gas heater 13 and the tail gas heat exchange of shell-side, be further cooled to 160～190 ℃ again, after be cooled to 60 ℃ through air cooler 14 successively, enter 1# gas-liquid separator 15 and carry out gas-liquid separation, tank deck conversion gas is cooled to 40 ℃ through water cooler 16, enter the further gas-liquid separation of 2# gas-liquid separator 17, the conversion gas of tank deck is sent and is carried hydrogen system 19 and do further processing, high-purity hydrogen (H more than final production 99.5mol%
2).At the bottom of 1# gas-liquid separator 15 and 2# gas-liquid separator 17 tanks, isolated process condensate send pump 18 to deliver to gas stripping column 1 after 20 preheatings of process condensate preheater by phlegma, and the process condensate after stripping process (PC) is delivered to out-of-bounds water treatment device.From oiler feed (BFW) shell-side of process feedwater preheater 12 and the conversion gas heat exchange intensification of pipe side successively out-of-bounds, after the reforming gas heat exchange of the shell-side of reforming gas water cooler 8 and pipe side is preheated to 200～260 ℃, deliver to again drum 5 and press saturation steam (5.2～5.6MPaG in by-product, 267～272 ℃), the middle pressure saturation steam conduct respectively of by-product, preheated oxygen, and the safe steam supplementing in oxygen pipeline, it is overheated that remaining steam send vapor superheater 10 to carry out, a steam part after overheated is as production labor skill steam, residue superheated vapour is delivered to battery limit (BL) outside ductwork.
The process furnace 6 that goes into operation arranging for initial start-up stage heat exchanger 7 without the gas mixture heating to tail gas+steam under thermal load condition, the gas mixture that is initial start-up stage tail gas+steam is heated to deliver to after 550～650 ℃ the unstripped gas entrance of converter 3 by the process furnace that goes into operation, after driving successfully, close go into operation process furnace 6 and relevant pipeline, by heat exchanger 7, utilize the thermal source that transforms generation to heat the tail gas of delivering to converter 3.
Native system goes out methane content in the reforming gas of converter and reaches below 0.6mol%, and the CO volume content after conversion gas is down to below 0.8mol%, through carrying the H after hydrogen system is processed
2content can reach 99.5mol%, has met device to high purity H
2requirement.
Claims (10)
1. a hydrocarbonaceous tail gas reforming hydrogen manufacturing technique, it is characterized in that, unstripped gas is sent into after being preheated to 110-130 ℃ in feed gas heater and delivered to after heat exchanger continues to be heated to 550～650 ℃ again and enter converter, going out reacted 950～1100 ℃ of high-temperature technology gases of converter sends in the useless pot of the conversion by-product that is connected with drum and presses saturation steam, process gas cooling is sent into after being down to 600～700 ℃ after heat exchanger and unstripped gas heat exchange successively, deliver to again after reforming gas water cooler and oiler feed heat exchange are cooled to 250～300 ℃ and send into shift converter, the variation temperature degree that goes out shift converter is 220～250 ℃, CO concentration is down to volume percent below 0.8%, described conversion gas is after feedwater preheater and feedwater heat exchange cooling, through feed gas heater and the further heat exchange of unstripped gas, be cooled to 160～190 ℃ again, then through air cooler, be cooled to 60 ℃ successively, enter 1# gas-liquid separator and carry out gas-liquid separation, the conversion gas that tank deck is drawn is cooled to 40 ℃ through water cooler and enters the further separation of 2# gas-liquid separator, the conversion pneumatic transmission that tank deck is drawn is carried hydrogen system and is done further processing, obtain high-purity hydrogen, described oiler feed is sent into reforming gas water cooler again and is preheated to 200～260 ℃ and sends into drum again after feedwater preheater and conversion gas heat exchange.
2. hydrocarbonaceous tail gas reforming hydrogen manufacturing technique as claimed in claim 1, it is characterized in that, described by drum, drawn in pressure saturation steam be divided into three strands, first strand to send vapor superheater to carry out overheated, as heating steam, send into oxygen preheat device for second strand and for preheating, enter the pure oxygen of converter, as safe steam, sneak in described pure oxygen for the 3rd strand.
3. hydrocarbonaceous tail gas reforming hydrogen manufacturing technique as claimed in claim 2, it is characterized in that, described shift converter is two-part shift converter, the temperature of one section outlet reaches 370 ℃～410 ℃ conversion gas, and through vapor superheater, to press saturation steam to carry out in to first strand overheated, then after demineralized-water preheater is cooled to 200～220 ℃, deliver to two sections of shift converters.
4. hydrocarbonaceous tail gas reforming hydrogen manufacturing technique as claimed in claim 3, it is characterized in that, in first strand, press saturation steam to press superheated vapour in forming after vapor superheater is overheated, be divided into two parts, a part is sent out-of-bounds middle pressure steam pipe network, and another part mixes with unstripped gas as process steam delivers to converter participation reaction after heat exchanger preheating.
5. the hydrocarbonaceous tail gas reforming hydrogen manufacturing technique as described in claims 1-4 any one, is characterized in that, while going into operation, the unstripped gas that goes out feed gas heater is first sent into after the process furnace that goes into operation is heated to 550～650 ℃ and sent into converter.
6. a hydrocarbonaceous tail gas reforming hydrogen manufacturing system, it is characterized in that, comprise converter, the outlet of described converter is successively through with the useless pot of the conversion of drum, heat exchanger, reforming gas water cooler, shift converter, feedwater preheater, feed gas heater, air cooler, 1# gas-liquid separator, water cooler, 2# gas-liquid separator and carry hydrogen system and be connected, and the unstripped gas entrance of described converter exports and is connected with the unstripped gas of feed gas heater through heat exchanger; The water inlet of described drum is connected with the water inlet of feedwater preheater through reforming gas water cooler.
7. hydrocarbonaceous tail gas reforming hydrogen manufacturing system as claimed in claim 6, is characterized in that, the oxygen intake of described converter is connected with the oxygen outlet of oxygen preheat device; The vapour outlet of described drum is communicated with steam-in, the steam-in of oxygen preheat device and the oxygen intake of converter of vapor superheater respectively.
8. hydrocarbonaceous tail gas reforming hydrogen manufacturing system as claimed in claim 7, is characterized in that, described shift converter is two-part shift converter, and one section outlet is connected with two sections of entrances through vapor superheater, demineralized-water preheater;
9. hydrocarbonaceous tail gas reforming hydrogen manufacturing system as claimed in claim 8, is characterized in that, the vapour outlet of described vapor superheater shell-side respectively with the unstripped gas entrance of heat exchanger shell-side and out-of-bounds middle pressure steam pipe network be communicated with.
10. the hydrocarbonaceous tail gas reforming hydrogen manufacturing system as described in claim 6-9, is characterized in that, the unstripped gas outlet of described feed gas heater is also connected with the unstripped gas entrance of converter through the process furnace that goes into operation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108275653A (en) * | 2018-03-22 | 2018-07-13 | 上海华林工业气体有限公司 | A kind of steam reformer flue gas heat recycling system and method |
| CN113620241A (en) * | 2021-08-20 | 2021-11-09 | 四川恒重清洁能源成套装备制造有限公司 | Natural gas hydrogen production system and process thereof |
| CN115465836A (en) * | 2022-09-05 | 2022-12-13 | 福建永荣科技有限公司 | Novel methanol hydrogen production process |
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| CN115465836A (en) * | 2022-09-05 | 2022-12-13 | 福建永荣科技有限公司 | Novel methanol hydrogen production process |
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| CN104058368B (en) | 2015-09-23 |
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