CN112499584A - Process for preparing hydrogen-nitrogen synthesis gas from desorption gas - Google Patents
Process for preparing hydrogen-nitrogen synthesis gas from desorption gas Download PDFInfo
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- CN112499584A CN112499584A CN202011600777.3A CN202011600777A CN112499584A CN 112499584 A CN112499584 A CN 112499584A CN 202011600777 A CN202011600777 A CN 202011600777A CN 112499584 A CN112499584 A CN 112499584A
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- 239000007789 gas Substances 0.000 title claims abstract description 138
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 238000003795 desorption Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 10
- 230000023556 desulfurization Effects 0.000 claims abstract description 10
- 238000006392 deoxygenation reaction Methods 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 9
- 229940045803 cuprous chloride Drugs 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- 238000010248 power generation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 10
- 230000002194 synthesizing effect Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 1
- 239000000571 coke Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000005261 decarburization Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000009798 Shen-Fu Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
Abstract
The application discloses a process for preparing hydrogen-nitrogen synthesis gas from desorption gas, relates to the technical field of synthesis gas preparation, and solves the technical problems of high process cost, high operation cost and the like of ammonia synthesis by separating nitrogen through an air separation process in the prior art. The process for preparing the hydrogen-nitrogen synthesis gas by the desorption gas comprises the following steps: raising the pressure of desorbed gas generated by the crude gas in the hydrogen production purification stage to a preset pressure value; carrying out fine desulfurization and fine deoxygenation treatment on the desorbed gas; subjecting the desorption gas to pressure swing adsorption to remove impurity gases except hydrogen and nitrogen to obtain a product gas; and synthesizing ammonia by using the product gas and hydrogen in a proper ratio. By adopting the technology for preparing the hydrogen-nitrogen synthesis gas by using the desorption gas, the investment and the operation cost of an air separation device are reduced.
Description
Technical Field
The application relates to the technical field of ammonia gas preparation, in particular to a process for preparing hydrogen-nitrogen synthesis gas from desorption gas.
Background
The semi-coke is prepared by low-temperature dry distillation of high-quality Jurasol clean coal blocks produced in Shenfu coal fields, and has the characteristics of high fixed carbon, high specific resistance, high chemical activity, low ash content, low aluminum content, low sulfur content and low phosphorus content.
The coal briquette can generate raw coke oven gas in the process of dry distillation, and the raw coke oven gas mainly contains hydrogen, carbon monoxide, carbon dioxide, nitrogen, oxygen, methane, hydrocarbons and the like. Coal chemical enterprises generally use raw coke oven gas as a raw material and adopt a process of purification after pressure swing adsorption to prepare hydrogen. The desorbed gas produced by the hydrogen production from the raw gas is generally used as fuel.
However, in the conventional process for synthesizing ammonia, nitrogen gas is separated from air and then reacted with hydrogen gas to synthesize ammonia. The process cost for synthesizing ammonia by separating nitrogen by adopting the air separation process is higher, and the safety risk of storage and transportation of pure oxygen produced by air separation is higher.
Disclosure of Invention
The embodiment of the invention provides a process for preparing hydrogen-nitrogen synthesis gas from desorption gas, and solves the technical problems that the process for synthesizing ammonia by separating nitrogen by adopting an air separation process in the prior art is high in cost, and the safety risk of storage and transportation of pure oxygen produced by air separation is high.
The process for preparing the hydrogen-nitrogen synthesis gas by using the desorption gas provided by the embodiment of the invention comprises the following steps:
raising the pressure of desorbed gas generated by the crude gas in the hydrogen production purification stage to a preset pressure value;
carrying out fine desulfurization and fine deoxygenation treatment on the desorbed gas;
carrying out pressure swing adsorption on the desorption gas to remove carbon monoxide and carbon dioxide to obtain a product gas;
ammonia is synthesized using the product gas.
In one possible implementation, the adsorbents used in the pressure swing adsorption of the desorbed gas include activated carbon, molecular sieves, and cuprous chloride loaded adsorbents.
In one possible implementation, the pressure swing adsorption of the stripping gas comprises the following steps: adsorption, pressure equalizing and reducing, reverse releasing, vacuumizing and boosting.
In a possible implementation manner, carbon monoxide and carbon dioxide adsorbed in the desorption gas in the pressure swing adsorption process are subjected to vacuum desorption and then are conveyed to a fuel pipe network, and then conveyed to a pyrolysis furnace or used for power generation.
In one possible implementation manner, the process for preparing hydrogen-nitrogen synthesis gas from desorbed gas further comprises: before the product gas enters an ammonia synthesis device, the product gas is refined and decarbonized, and the refining process comprises the processes of conversion and methanol washing.
In a possible implementation, the preset pressure value is greater than 0.6 MPa.
In one possible implementation manner, the process for preparing hydrogen-nitrogen synthesis gas from desorbed gas further comprises: and (3) supplementing hydrogen from the outside to ensure that the hydrogen-nitrogen ratio in the mixed gas is 3: 1.
One or more technical solutions provided in the embodiments of the present invention have at least the following technical effects or advantages:
the embodiment of the invention provides a process for preparing hydrogen-nitrogen synthesis gas from desorption gas, wherein the desorption gas generated after the raw gas is used for preparing hydrogen contains gases such as nitrogen, hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, oxygen, methane and the like, the desorption gas is subjected to fine desulfurization and fine deoxygenation after being pressurized to a preset pressure value, the hydrogen sulfide and the oxygen in the desorption gas can be removed, then the desorption gas is subjected to pressure swing adsorption, the carbon monoxide and the carbon dioxide in the desorption gas can be removed, further a product gas is obtained, the product gas mainly comprises nitrogen, hydrogen and methane, and then the product gas is used for synthesizing ammonia. By adopting the technology for preparing the hydrogen-nitrogen synthesis gas by using the desorption gas, the investment and the operation cost of an air separation device are reduced, and the safety risk of storage and transportation of pure oxygen produced by air separation is avoided.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a block diagram of a syngas production process provided by an embodiment of the present application;
FIG. 2 is a flow diagram of a syngas production process provided by an embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 and fig. 2, an embodiment of the present invention provides a process for preparing hydrogen-nitrogen synthesis gas from desorption gas, where the process for preparing hydrogen-nitrogen synthesis gas from desorption gas includes steps S201 to S204.
Step S201, raising the pressure of desorbed gas generated by the crude gas in the hydrogen production purification stage to a preset pressure value.
And step S202, carrying out fine desulfurization and fine deoxygenation treatment on the desorbed gas.
And step S203, performing pressure swing adsorption on the desorbed gas to remove carbon monoxide and carbon dioxide to obtain a product gas.
And step S204, synthesizing ammonia by using the product gas.
As shown in fig. 1, the desorbed gas input from the left side is the desorbed gas generated after the crude gas is used for hydrogen production, the pressure of the desorbed gas is low, and the pressure of the desorbed gas reaches a preset pressure value through pressure increase. The preset pressure value is associated with a subsequent desulfurization and deoxidation working section and a subsequent decarburization working section. For example, the preset pressure value may be set to be greater than 0.6 MPa.
The desorbed gas after being pressurized enters a desulfurization and deoxidation section, and the step S202 is carried out in the desulfurization and deoxidation section to carry out deoxidation and desulfurization treatment on the desorbed gas, so that hydrogen sulfide and oxygen in the desorbed gas can be removed.
And (3) the desorbed gas after desulfurization and deoxidation treatment enters a decarburization working section, step S203 is carried out in the decarburization working section, and the desorbed gas is subjected to pressure swing adsorption to remove carbon monoxide and carbon dioxide and obtain a product gas. The total content of hydrogen and nitrogen in the product gas accounted for 99.99% (volume fraction) of the product gas.
And (3) after the product gas is output from the decarburization working section, step S204 is implemented, the product gas is used for synthesizing ammonia, and nitrogen and hydrogen in the product gas are subjected to chemical reaction to generate ammonia gas. Because the hydrogen content in the product gas is less, the hydrogen can be supplemented from the outside, so that the nitrogen-hydrogen ratio after the hydrogen is supplemented is 3: after 1, ammonia synthesis is carried out, so that nitrogen in the product gas can be fully utilized.
By implementing the technology for preparing the hydrogen-nitrogen synthesis gas from the desorption gas provided by the embodiment of the invention, the investment and the operation cost of an air separation device are reduced, and the safety risk of storage and transportation of pure oxygen produced by air separation is avoided.
Specifically, when the desorbed gas is subjected to pressure swing adsorption, the desorbed gas is introduced into a pressure swing adsorption decarbonization device, and an adsorbent is contained in the pressure swing adsorption decarbonization device and can adsorb carbon monoxide and carbon dioxide in the desorbed gas. Since the molecular weight of carbon monoxide and the molecular weight of nitrogen are both 28, carbon monoxide is adsorbed by using a conventional adsorbent, nitrogen is also adsorbed, and nitrogen and carbon monoxide cannot be effectively separated. The adsorbent used for pressure swing adsorption of the desorbed gas provided by the embodiment of the invention comprises activated carbon, a molecular sieve and a cuprous chloride loaded adsorbent.
The cuprous chloride supported adsorbent has a strong adsorption effect on carbon monoxide molecules and a weak adsorption effect on nitrogen molecules, and carbon monoxide in the learning gas can be removed by using the cuprous chloride supported adsorbent.
The cuprous chloride supported adsorbent in the embodiment refers to a molecular sieve loaded with cuprous chloride. For example, the cuprous chloride supported adsorbent can be prepared by mixing CuCl and gamma-Al2O3And 4A, 13X, NaY, Cu+And (3) mixing and heating the molecular sieves such as the Y grade and the like respectively to obtain the adsorbent.
The activated carbon and the molecular sieve in the adsorbent used in the pressure swing adsorption can effectively remove the carbon dioxide in the desorbed gas.
Step S203 is implemented in the decarburization section, and when the desorbed gas is subjected to pressure swing adsorption, the method comprises the following steps: adsorption, pressure equalizing and reducing, reverse releasing, vacuumizing and boosting.
With continued reference to fig. 1, the high calorific desorption gas illustrated in fig. 1 is carbon monoxide and carbon dioxide that are adsorbed during the pressure swing adsorption process, and these adsorbed carbon monoxide and carbon dioxide are vacuum desorbed and then delivered to a fuel piping network and then to a pyrolysis furnace or for power generation. After the high-calorific-value desorption gas is conveyed to the pyrolysis furnace, carbon monoxide is combusted in the pyrolysis furnace to dry-distill the coal briquettes, so that the carbon monoxide is effectively utilized, and the waste is avoided.
The process for preparing the hydrogen-nitrogen synthesis gas by using the desorption gas further comprises the following steps: before the product gas is introduced into the ammonia synthesis device, the product gas is refined and decarbonized to remove residual carbon monoxide and carbon dioxide in the product gas. The refining process includes shift conversion and methanol washing processes. After the refining process flow, the content of carbon monoxide and carbon dioxide in the product gas is further reduced, and the product gas can meet the requirement of synthetic ammonia.
With continued reference to fig. 1, the process for producing hydrogen-nitrogen syngas from stripping gas further comprises: supplying hydrogen from outside to the ammonia synthesis device to make the ratio of hydrogen to nitrogen in the mixed gas be 3: 1.
After the product gas is directly used for synthesizing ammonia, a large amount of unreacted nitrogen exists in the ammonia gas, so that the waste of the nitrogen gas is caused, and the purity of the ammonia gas is low. The hydrogen is introduced into the product gas from the outside to ensure that the hydrogen-nitrogen ratio in the product gas is 3:1, and then the ammonia is synthesized, so that the nitrogen is fully utilized, and the purity of the ammonia is greatly improved. Wherein, the externally supplemented hydrogen can be hydrogen prepared from raw coke oven gas, so that the raw coke oven gas can be fully utilized.
The embodiments in the present specification are described in a progressive manner, and the same or similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure.
Claims (7)
1. A process for preparing hydrogen-nitrogen synthesis gas by using desorption gas is characterized by comprising the following steps:
raising the pressure of desorbed gas generated by the crude gas in the hydrogen production purification stage to a preset pressure value;
carrying out fine desulfurization and fine deoxygenation treatment on the desorbed gas;
removing carbon monoxide and carbon dioxide from the desorbed gas by pressure swing adsorption to obtain a product gas;
ammonia is synthesized using the product gas.
2. The process for preparing hydrogen-nitrogen synthesis gas from desorbed gas as claimed in claim 1, wherein the adsorbents used in the pressure swing adsorption of the desorbed gas comprise activated carbon, molecular sieve and cuprous chloride loaded adsorbent.
3. The process for preparing hydrogen-nitrogen synthesis gas from desorbed gas as claimed in claim 1, wherein the pressure swing adsorption of the desorbed gas comprises the following steps: adsorption, pressure equalizing and reducing, reverse releasing, vacuumizing and boosting.
4. The process for preparing hydrogen-nitrogen synthesis gas from desorbed gas according to claim 1, wherein carbon monoxide and carbon dioxide adsorbed in the desorbed gas during pressure swing adsorption are desorbed in vacuum and then transported to a fuel pipe network, and then transported to a pyrolysis furnace or used for power generation.
5. The process for preparing hydrogen and nitrogen synthesis gas from desorption gas as claimed in claim 1, further comprising refining and decarbonizing the product gas before the product gas enters an ammonia synthesis device, wherein the refining process comprises shift conversion and methanol washing processes.
6. The process for preparing hydrogen-nitrogen synthesis gas from desorbed gas as claimed in claim 1, wherein the preset pressure value is greater than 0.6 MPa.
7. The process for preparing the hydrogen-nitrogen synthesis gas from the desorption gas as claimed in claim 1, further comprising supplementing hydrogen from the outside so that the hydrogen-nitrogen ratio in the mixed gas is 3: 1.
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| CN202011600777.3A CN112499584A (en) | 2020-12-30 | 2020-12-30 | Process for preparing hydrogen-nitrogen synthesis gas from desorption gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184805A (en) * | 2021-04-27 | 2021-07-30 | 陕西东鑫垣化工有限责任公司 | Comprehensive utilization and carbon fixation process for pyrolysis gas |
| CN113830735A (en) * | 2021-11-23 | 2021-12-24 | 清华大学 | Medium-temperature purification hydrogen production method and equipment for reforming hydrocarbon fuel and fuel cell energy supply system |
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| CN113830735A (en) * | 2021-11-23 | 2021-12-24 | 清华大学 | Medium-temperature purification hydrogen production method and equipment for reforming hydrocarbon fuel and fuel cell energy supply system |
| CN113830735B (en) * | 2021-11-23 | 2022-07-12 | 清华大学 | Medium-temperature purification hydrogen production method and equipment for reforming hydrocarbon fuel and fuel cell energy supply system |
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Application publication date: 20210316 |