CN103803492B - The method of low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG - Google Patents
The method of low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG Download PDFInfo
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- CN103803492B CN103803492B CN201410054505.6A CN201410054505A CN103803492B CN 103803492 B CN103803492 B CN 103803492B CN 201410054505 A CN201410054505 A CN 201410054505A CN 103803492 B CN103803492 B CN 103803492B
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Abstract
A kind of method that the invention discloses low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG, first will pressurize at the beginning of coal gas elder generation removing dust and be divided into 2 parts after compression, a part, after desulfurization, conversion and transformationreation, carries out PSA and carries hydrogen, and another is respectively used to direct hydrogen production and prepares hydrogen coproduction LNG.The method can according to hydrogen amount number, flexible hydrogen output, have investment and operating cost is low, energy consumption is low, capacity usage ratio advantages of higher.
Description
Technical field
The invention belongs to coal gas deep process technology field, particularly to a kind of method of low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG.
Background technology
The processing use procedure of coal there is substantial amounts of coal gas (such as coking, dry distilling, pyrolysis etc.), containing CH in coal gas4、H2, a large amount of useful resources such as CO and H2The harmful components such as S, COS, if directly simple combustion is fallen, not only utilization ratio is low, also can cause environmental pollution.Therefore, the coal gas produced in Coal Chemical Industry process is carried out deep processing and utilization to have very important significance.
The mode that coal gas utilizes mainly has following several: the coal gas produced for major part coke-oven plant, after removing dust, cooling, pressurization, purification, returns coke oven combustion chamber burning and utilizes；Also part coal plant is had first to be converted by coal gas, then as F-T synthesis unstripped gas；Or coal gas is used as industrial chemicals and produces the chemical products such as methanol；Or coal gas is carried out carrying hydrogen, produces hydrogen and LNG(liquefied natural gas) product.
Gas methanation is produced LNG, have investment little, consume the advantages such as low, pollution-free, capacity usage ratio is high, product market prospect is good；Can also, according to enterprise's concrete condition, for needing hydrogen technical process to produce coproduction LNG while hydrogen, be the preferably selection that utilizes of coal gas.Carry in the technique of hydrogen at coal gas LNG, coal gas, mostly take first to put forward the mode of deep cooling after hydrogen at present, although decrease subzero treatment amount, but add cost of investment；Or directly adopting PSA to put forward hydrogen technology, the comprehensive method of investment is higher.
Summary of the invention
The present invention provides a kind of method of low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG, and based on the coal gas that low-temperature pyrolysis of coal produces, investment is with operating cost is low, energy consumption is low, capacity usage ratio is high.
Realize above-mentioned purpose to be adopted the technical scheme that: a kind of method of low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG, comprise the steps of
(1) by pressurization at the beginning of coal gas elder generation removing dust and compression, then it is divided into 2 parts according to the target hydrogen output set, is respectively used to direct hydrogen production and prepares hydrogen co-production LNG；
(2) by a part of coal gas of step (1) gained, after carrying out desulfurization, conversion and transformationreation, carry out PSA and carry hydrogen, prepare pure hydrogen production；
(3) by another part coal gas of step (1) gained, advanced line translation reaction, CO is transformed to H2And CO2, carry out low-temperature rectisol decarburization afterwards, prepare and purify pneumatic transmission cryogenic separation, after separation, obtain hydrogen and LNG product.
In described step (1), first pressue device uses helical-lobe compressor, and compressor uses reciprocating compressor.
In described step (2), it is preferable that desulfurization adopts dry desulfurization, desulfurizing agent adopts zinc oxide or middle temperature iron-manganese desulfurizer.
In described step (2), (3), at shift conversion step, adopt sulphur resisting and low temp conversing technology, temperature be 180～360 DEG C, pressure be 1～8MPa when, complete CO transformationreation and obtain conversion gas.
In described step (3), hydrogen cryogenic separation gone out send PSA to carry hydrogen production device and purifies further.
The present invention adopts helical-lobe compressor to carry out just pressurization and reciprocating compressor and is compressed, and the method carrying hydrogen after adopting first deep cooling, investment and operating cost is low, energy consumption is low, capacity usage ratio is high.It also have the advantage that
1, can according to the number of hydrogen amount, flexible hydrogen output；
2, PSA carries hydrogen unit, and to be placed in whole technological process last, unstripped gas sequentially passes through purifier, liquefaction segregation apparatus and PSA and carries hydrogen production device, avoid PSA in existing technique and carry the Vacuum solutions gassing (namely being carried the adsorbed high methane gas of hydrogen production device by PSA) of hydrogen production device, need secondary booster to meet the postorder high methane gas liquefaction and separation system situation to pressure requirements, eliminate second-compressed system, decrease unnecessary power consumption, overall investment and operating cost and all have bigger reduction；
3, can producing hydrogen and LNG, both has significantly high market value simultaneously, it is also possible to meeting other needs the hydrogen project demand to hydrogen.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described further:
Fig. 1 is the process chart of the present invention；
Fig. 2 is the process chart of embodiment 3.
Detailed description of the invention
Referring to Fig. 1, the method for the low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG of the present invention, comprise the steps of
(1) by coal gas elder generation removing dust, using helical-lobe compressor to carry out just pressurization, re-use reciprocating compressor and be compressed, then according to the target hydrogen output set is divided into 2 parts, a part of direct hydrogen production, another part prepares hydrogen co-production LNG product；
(2) by a part of coal gas of step (1) gained, after first carrying out desulfurization, conversion and transformationreation, deliver to PSA device for producing hydrogen and carry hydrogen, prepare pure hydrogen production；Described desulfurization can adopt dry desulfurization, and desulfurizing agent adopts zinc oxide or middle temperature iron-manganese desulfurizer.Described gas reforming, under catalyst existent condition, can make the CH in coal gas4Generation CO and H is reacted with the steam in injected system2；The CO that conversion is generated by described shift conversion step connects the CO in raw material coal gas and adopts sulphur resisting and low temp conversing technology, temperature be 180～360 DEG C, pressure be 1～8MPa when, complete CO transformationreation and obtain conversion gas, in this process, CO, through conversion, reacts generation CO with steam2And H2, thus improve the yield of hydrogen；Obtaining product hydrogen after PSA purifies, the purity of this product hydrogen is up to more than 99.95%；
(3) by another part coal gas of step (1) gained, first adopt sulphur resisting and low temp conversing technology, temperature be 180～360 DEG C, pressure be 1～8MPa when, complete CO transformationreation and obtain conversion gas, be transformed to H by CO2And CO2；Carrying out low-temperature rectisol decarburization afterwards, prepared purge gas carries out cryogenic separation, obtains hydrogen and LNG product after separation.The hydrogen that described cryogenic separation goes out send PSA to carry hydrogen production device and purifies further.For ensureing that product hydrogen purity reaches more than 99.95%, the cryogenic liquefying of unstripped gas separates can adopt hybrid refrigeration liquefaction process and cryogenic rectification separating technology.It is about to purify qualified unstripped gas and enters liquefaction separative element, liquefy in ice chest, and by means of foreign gases such as the two-tower rectification flow process separating hydrogen gas of high and low pressure rectifying column, carbon monoxide, nitrogen.Wherein, liquefaction ice chest institute chilling requirement is provided by mixed-refrigerant cycle system, and mix refrigerant is by C1～C5 and N2(it is generally selected from C1, C2, C3, C4 and C5 alkane and N2In four kinds, five kinds or six kinds, they are according to arbitrary volume ratio or according to about equivalent volume ratio) composition, utilize and the ice chest that do not coexist of each component boiling point cools down and after choke valve throttling, cooling, the cold end of ice chest is returned as the cold-producing medium that backflows, once cool down the unstripped gas of different warm area and just flowing cold-producing medium, after cold-producing medium re-heat of backflowing, returning to mix refrigerant compressor compresses.
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The method of the present embodiment low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG is, certain low temperature pyrogenation coal gas, and it becomes to be grouped in Table 1, and design coal gas treating capacity is 2.0 × 105Nm3/ h, target needs hydrogen amount to be 1.02 × 105Nm3/ h, dividing two parts coal gas percent by volume accordingly is 12% 88%, carries out thermal center by respective flow process respectively.After raw material coal gas elder generation removing dust, just pressurization (employing helical-lobe compressor) and compression (employing reciprocating compressor), a part (12%) is after dry desulfurization, after methane reformers, carbon monoxide conversion device, is sent to PSA and carries hydrogen production device extraction hydrogen.Another part (88%) is sent to after converting means carries out carbon monodixe conversion, carry out low-temperature rectisol elimination sour gas, being sent to cryogenic separation device be easily separated, prepare hydrogen and LNG product, hydrogen cryogenic separation gone out send PSA to carry hydrogen production device and purifies further.In products obtained therefrom, hydrogen product purity is 99.98%, and in LNG product, methane volumetric degree is 92.3%, and the total specific energy consumption of LNG is 0.51kW h/Nm3。
Table 1 low temperature pyrogenation coal gas forms
| Component | Vol% |
| H2 | 26.7845 |
| CO | 17.297 |
| CO2 | 10.109 |
| CH4 | 38.7214 |
| N2 | 2.3373 |
| O2 | 0.624 |
| C2H4 | 0.7835 |
| C2H6 | 3.3321 |
| H2O(gas) | 0 |
| H2S | 0.011 |
Embodiment 2
The method of the present embodiment low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG is, certain low temperature pyrogenation coal gas, and it becomes to be grouped in Table 2, and design coal gas treating capacity is 2.0 × 105Nm3/ h, target needs hydrogen amount to be 1.48 × 105Nm3/ h, dividing two parts coal gas percent by volume accordingly is 34% 66%.After this coal gas elder generation removing dust, first pressurization (use helical-lobe compressor) and compression (use reciprocating compressor), a part (34%) is after dry desulfurization, after methane reformers, carbon monoxide conversion device, is sent to PSA and carries hydrogen production device extraction hydrogen.Another part (66%) is sent to after converting means carries out carbon monodixe conversion, carry out low-temperature rectisol elimination sour gas, being sent to cryogenic separation device be easily separated, prepare hydrogen and LNG product, hydrogen cryogenic separation gone out send PSA to carry hydrogen production device and purifies further.In products obtained therefrom, hydrogen product purity reaches 99.96%, and in LNG product, methane volumetric degree is 89.7%, and the total specific energy consumption of LNG is 0.46kW h/Nm3。
Table 2 low temperature pyrogenation coal gas forms
| Component | Vol% |
| H2 | 30.65 |
| CO | 16.37 |
| CO2 | 10.13 |
| CH4 | 35.64 |
| N2 | 4.22 |
| O2 | 0.76 3 --> |
| C2H4 | 0.68 |
| C2H6 | 1.54 |
| H2O(gas) | 0.002 |
| H2S | 0.0081 |
Embodiment 3
Referring to Fig. 2, the method for the present embodiment low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG is, certain low temperature pyrogenation coal gas, and its composition is in Table 3, and design coal gas treating capacity is 2.0 × 105Nm3/ h, target needs hydrogen amount to be 7.42 × 104Nm3/ h, then coal gas need not be divided into two parts accordingly, directly by this coal gas elder generation removing dust, just pressurization (use helical-lobe compressor) and compression (use reciprocating compressor), it is sent to after converting means carries out carbon monodixe conversion, carry out low-temperature rectisol elimination sour gas, being sent to cryogenic separation device be easily separated, prepare hydrogen and LNG product, hydrogen cryogenic separation gone out send PSA to carry hydrogen production device and purifies further.In products obtained therefrom, hydrogen product purity reaches 99.99%, and in LNG product, methane volumetric degree is 96%, and the total specific energy consumption of LNG is 0.49kW h/Nm3。
Table 3 low temperature pyrogenation coal gas forms
| Component | Vol% |
| H2 | 24.65 |
| CO | 18.37 |
| CO2 | 7.13 |
| CH4 | 44.15 |
| N2 | 2.67 |
| O2 | 1.22 |
| C2H4 | 0.34 |
| C2H6 | 1.42 |
| H2O(gas) | 0.005 |
| H2S | 0.031 |
Below it is only the better embodiment of the present invention, not the present invention is done any pro forma restriction, the equivalent variations embodiment that the technology contents of the disclosure above is made by any technical staff, in every case it is the content without departing from technical solution of the present invention, according to any simple modification, equivalent variations and modification that above-described embodiment is done by the technical spirit of the present invention, all still fall within the scope of technical solution of the present invention.
Claims (4)
1. the method for a low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG, it is characterised in that: comprise the steps of
(1) by pressurization at the beginning of coal gas elder generation removing dust and compression, then it is divided into 2 parts according to the target hydrogen output set, is respectively used to direct hydrogen production and prepares hydrogen co-production LNG；
(2) by a part of coal gas of step (1) gained, after carrying out desulfurization, conversion and transformationreation, carry out PSA and carry hydrogen, prepare pure hydrogen production；
(3) by another part coal gas of step (1) gained, advanced line translation reaction, CO is transformed to H2And CO2, carry out low-temperature rectisol decarburization afterwards, prepare and purify pneumatic transmission cryogenic separation, after separation, obtain hydrogen and LNG product；
In described step (1), first pressue device uses helical-lobe compressor, and compressor uses reciprocating compressor.
2. the method for low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG as claimed in claim 1, it is characterised in that: in described step (2), it is preferable that desulfurization adopts dry desulfurization, desulfurizing agent adopts zinc oxide or middle temperature iron-manganese desulfurizer.
3. the method for low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG as claimed in claim 1, it is characterized in that: in described step (2), (3), at shift conversion step, adopt sulphur resisting and low temp conversing technology, temperature be 180～360 DEG C, pressure be 1～8MPa when, complete CO transformationreation and obtain conversion gas.
4. the method for low temperature pyrogenation coal gas hydrogen manufacturing cogeneration LNG as claimed in claim 1, it is characterised in that: in described step (3), hydrogen cryogenic separation gone out send PSA to carry hydrogen production device and purifies further.
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| CN104987887B (en) * | 2015-08-05 | 2017-06-27 | 华陆工程科技有限责任公司 | The method for producing coal tar and synthesis gas as raw material with rich oil coal |
| CN105238471B (en) * | 2015-10-19 | 2017-12-01 | 中国华能集团清洁能源技术研究院有限公司 | A kind of low temperature distillation coal gas preparing natural gas co-production LPG system |
| CN105419871A (en) * | 2015-12-24 | 2016-03-23 | 袁峥嵘 | Method of producing hydrogen through fixed bed pressurized continuous gasification |
| CN107014151B (en) * | 2017-06-01 | 2023-04-11 | 四川蜀道装备科技股份有限公司 | Device and method for liquefying hydrogen |
| CN108117047B (en) * | 2017-12-22 | 2020-02-28 | 新疆宣力环保能源有限公司 | Low-pressure sulfur-tolerant shift and special adsorbent inerting-discharging technology for hydrogen production from raw gas |
| CN112678773B (en) * | 2020-12-28 | 2022-12-27 | 成都益志科技有限责任公司 | Process for producing hydrogen and coproducing LNG (liquefied Natural gas) by using raw gas |
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