CN114804025B - Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming - Google Patents
Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming Download PDFInfo
- Publication number
- CN114804025B CN114804025B CN202210500804.2A CN202210500804A CN114804025B CN 114804025 B CN114804025 B CN 114804025B CN 202210500804 A CN202210500804 A CN 202210500804A CN 114804025 B CN114804025 B CN 114804025B
- Authority
- CN
- China
- Prior art keywords
- gas
- methanol
- inlet
- outlet
- ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 270
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 69
- 238000002407 reforming Methods 0.000 title claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000005265 energy consumption Methods 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 114
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003546 flue gas Substances 0.000 claims abstract description 50
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002485 combustion reaction Methods 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 238000006057 reforming reaction Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 37
- 238000003786 synthesis reaction Methods 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 12
- 239000002918 waste heat Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 pharmacy Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention discloses a method and a system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming, comprising the following steps: s1, mixing methanol and water in a certain proportion, reforming, condensing and pressure swing adsorption to obtain pure hydrogen; s2, mixing the pressurized pure nitrogen with the pressurized pure hydrogen to perform a synthetic ammonia reaction, and rectifying a synthetic product to obtain pure ammonia; s3, performing pressure swing adsorption separation in S1 to obtain valve gas which contains carbon dioxide and a small amount of hydrogen as main components, mixing the valve gas with pure oxygen for combustion to generate high-temperature flue gas, condensing the high-temperature flue gas after the high-temperature flue gas provides heat for the reforming reaction in S1 to obtain high-purity carbon dioxide, and capturing carbon; compared with the traditional coal-to-ammonia system, the invention combines the methanol reforming hydrogen production and the air separation device, constructs a method and a system for preparing ammonia based on zero-energy-consumption carbon capture methanol, and provides a new scheme for realizing the aim of carbon neutralization in China.
Description
Technical Field
The invention belongs to the field of ammonia production by methanol reforming, and particularly relates to a method and a system for ammonia production by methanol reforming based on zero-energy-consumption carbon capture.
Background
Ammonia is an important raw material and is widely applied to the fields of chemical industry, light industry, chemical fertilizer, pharmacy, synthetic fiber and the like, so that the demand of the ammonia is increasing. The existing industrial synthesis method of ammonia gas mainly adopts hydrogen and nitrogen to react and synthesize at high temperature (450-500 ℃), high pressure (20-30 MPa) and the presence of a catalyst.
Conventional ammonia systems that use reformed natural gas to provide the hydrogen required for the ammonia process and coal as the fuel suffer from the following drawbacks: the temperature conditions required for the reforming reaction of natural gas are relatively high (750-1000 ℃), and therefore relatively high energy consumption is generally required; solid material treatment and desulfurization treatment are needed to be carried out in the subsequent combustion of coal, and the concentration of carbon dioxide in the flue gas is low, so that the energy consumption for carbon capture is high. Therefore, finding a zero-energy-consumption carbon capture ammonia production system with high-efficiency waste heat utilization and comprehensive economic consideration is a current urgent problem to be solved.
Disclosure of Invention
Therefore, the invention aims to solve the problems and provide the method and the system for preparing ammonia by reforming the methanol based on zero-energy-consumption carbon capture, which have the advantages of simple structure, high efficiency, low production cost, long service life and environmental friendliness.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a method for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming comprises the following steps:
s1, mixing methanol and water in a certain proportion, reforming, condensing and pressure swing adsorption to obtain pure hydrogen;
s2, mixing the pressurized pure nitrogen with the pressurized pure hydrogen to perform a synthetic ammonia reaction, and rectifying a synthetic product to obtain pure ammonia;
and S3, performing pressure swing adsorption separation in S1 to obtain valve gas which contains carbon dioxide and a small amount of hydrogen as main components, mixing and burning the valve gas and pure oxygen to generate high-temperature flue gas, and condensing the high-temperature flue gas after the high-temperature flue gas provides heat for the reforming reaction in S1 to obtain high-purity carbon dioxide and collecting carbon.
Further, in S1, the mixture of methanol and water is preheated by using the residual heat of the reformed first synthesis gas.
Further, the second synthesis gas obtained by the synthesis ammonia reaction in S2 provides heat for the reforming reaction in S1.
Further, after the high-temperature flue gas burnt by the valve gas in the step S3 provides heat for the reforming reaction in the step S1, the waste heat provides heat for the mixture of methanol and water before entering the methanol reforming reactor.
The invention also provides a system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming, which comprises a first mixer, a second heat exchanger, a methanol reforming reactor, a first condenser, a pressure swing adsorber, a first gas compressor, a second gas compressor, a synthetic ammonia reactor, a rectifying tower, a combustion chamber and a second condenser, wherein the first mixer is provided with a methanol inlet and a water inlet which are respectively connected with a methanol conveying pipeline and a water supply pipeline, an outlet of the first mixer is connected with an inlet on the cold side of the second heat exchanger for heating a mixture of methanol and water, an outlet on the cold side of the second heat exchanger is connected with an inlet of the methanol reforming reactor, so that methanol and water are subjected to reforming reaction in the methanol reforming reactor to generate first synthetic gas, an outlet of the methanol reforming reactor is connected with an inlet of the first condenser, an outlet of the first condenser is connected with the pressure swing adsorber, and the first synthetic gas is subjected to pressure swing adsorption to obtain pure hydrogen, and an outlet of the pressure swing adsorber is connected with an inlet of the first gas compressor; the inlet of the second gas compressor is connected with a nitrogen source, the synthetic ammonia reactor is respectively connected with the outlet of the first gas compressor and the outlet of the second gas compressor, the synthetic ammonia reaction is carried out in the synthetic ammonia reactor to obtain second synthetic gas, the outlet of the synthetic ammonia reactor is connected with the inlet of the rectifying tower, and the second synthetic gas is rectified to obtain pure ammonia gas;
the combustion chamber is respectively connected with a valve gas outlet of the pressure swing adsorber and an oxygen source, a flue gas outlet of the combustion chamber is connected with the methanol reforming reactor, high-temperature flue gas generated by combustion provides a heat source for reforming reaction, and the flue gas after heat exchange is condensed by the second condenser to obtain high-purity carbon dioxide and carbon capture is carried out on the carbon dioxide.
Further, the device also comprises a first heat exchanger, wherein the first mixer is connected with the second heat exchanger through a mixed fluid pipeline, and the mixed fluid pipeline is connected with the cold side of the first heat exchanger, so that the first heat exchanger preheats the mixture of methanol and water; the methanol reforming reactor is connected with the first condenser through a first synthesis gas pipeline, and the first synthesis gas pipeline is connected with the hot side of the first heat exchanger and used as a heat source of the first heat exchanger.
Further, the device also comprises a second mixer and a third mixer, wherein the second mixer is provided with a hydrogen inlet and a nitrogen inlet, and is respectively connected with the outlet of the first gas compressor and the outlet of the second gas compressor, and the outlet of the second mixer is connected with the mixed gas inlet of the synthetic ammonia reactor; the third mixer is provided with a valve gas inlet and an oxygen inlet which are respectively connected with a valve gas outlet and an oxygen source of the pressure swing adsorber, and an outlet of the third mixer is connected with an inlet of the combustion chamber.
The second mixer is used for uniformly mixing the hydrogen and the nitrogen, so that the reaction efficiency of synthesizing ammonia from the hydrogen and the nitrogen is improved.
The third mixer is used for uniformly mixing the valve gas and the oxygen so as to enable the valve gas to burn more thoroughly.
Further, the synthetic ammonia reactor is connected with the rectifying tower through a second synthetic gas pipeline, and the second synthetic gas pipeline is connected with the methanol reforming reactor to provide a heat source for reforming reaction.
Further, the combustion chamber outlet is connected with the flue gas inlet of the methanol reforming reactor through the front section of the flue gas pipeline, and the flue gas outlet of the methanol reforming reactor is connected with the inlet of the second condenser through the rear section of the flue gas pipeline, wherein the rear section of the flue gas pipeline is connected with the hot side of the second heat exchanger.
Further, the nitrogen source and the oxygen source are both from the same air separation device, nitrogen and oxygen are separated from air through the air separation device, and respectively enter the synthesis ammonia reactor and the combustion chamber. Of course, the route of obtaining the nitrogen and the oxygen is not limited thereto, and other devices capable of achieving equivalent effects may be substituted.
The technical scheme provided by the invention has the following beneficial effects:
1. compared with natural gas reforming hydrogen production, the methanol reforming hydrogen production can be carried out at medium and low temperature (250-300 ℃), and the hydrogen production realized by only relying on internal waste heat has great potential;
2. the introduction of the air separation device provides a nitrogen raw material for the preparation of synthetic ammonia, and simultaneously pure oxygen combustion is possible, so that only carbon dioxide and water vapor are contained in the flue gas after combustion, and the flue gas after combustion can be condensed to obtain high-purity carbon dioxide after passing through the waste heat recovery unit, thereby realizing zero-energy-consumption carbon capture.
3. Realizing the full utilization of waste heat of different grades in the system and greatly reducing the cost of the ammonia production process. The low-concentration hydrogen flow generated by pressure swing adsorption is combusted and converted, and the medium-temperature heat released in the ammonia preparation process is utilized to realize the ammonia preparation by means of the waste heat in the system.
Drawings
FIG. 1 is a process flow diagram of a system for reforming methanol to produce ammonia based on zero-energy carbon capture.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description.
A method for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming comprises the following steps:
s1, mixing methanol and water in a certain proportion, reforming, condensing and pressure swing adsorption to obtain pure hydrogen;
s2, mixing the pressurized pure nitrogen with the pressurized pure hydrogen to perform a synthetic ammonia reaction, and rectifying a synthetic product to obtain pure ammonia;
and S3, performing pressure swing adsorption separation in S1 to obtain valve gas which contains carbon dioxide and a small amount of hydrogen as main components, mixing and burning the valve gas and pure oxygen to generate high-temperature flue gas, and condensing the high-temperature flue gas after the high-temperature flue gas provides heat for the reforming reaction in S1 to obtain high-purity carbon dioxide and collecting carbon.
Further, in S1, the mixture of methanol and water is preheated by using the residual heat of the reformed first synthesis gas.
Further, the second synthesis gas obtained by the synthesis ammonia reaction in S2 provides heat for the reforming reaction in S1.
Further, after the high-temperature flue gas burnt by the valve gas in the step S3 provides heat for the reforming reaction in the step S1, the waste heat provides heat for the mixture of methanol and water before entering the methanol reforming reactor.
As shown in fig. 1, the system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming comprises a first mixer 1, a hydraulic pump 2, a first heat exchanger 3, a second heat exchanger 4, a methanol reforming reactor 5, a first condenser 6, a pressure swing adsorber 7, a first gas compressor 8, an air separation device 9, a second gas compressor 10, a second mixer 11, a synthesis ammonia reactor 12, a rectifying tower 13, a third mixer 14, a combustion chamber 15, a second condenser 16, a methanol delivery pipeline 17, a water supply pipeline 18, a mixed fluid pipeline 19, a first synthesis gas pipeline 20, a second synthesis gas pipeline 21, a first drainage pipeline 22, a hydrogen delivery pipeline 23, an air delivery pipeline 24, a nitrogen delivery pipeline 25, a first mixed gas pipeline 26, a third synthesis gas pipeline 27, an ammonia delivery pipeline 28, a valve gas delivery pipeline 29, an oxygen delivery pipeline 30, a first mixed gas pipeline 31, a flue gas pipeline 32, a second drainage pipeline 33 and a carbon dioxide delivery pipeline 34.
The methanol inlet and the water inlet of the first mixer 1 are respectively connected with a methanol conveying pipeline 17 and a water supply pipeline 18, the outlet of the first mixer 1 is connected with the inlet of a hydraulic pump 2 through a mixed fluid pipeline 19, and the outlet of the hydraulic pump 2 is connected with the inlet of the methanol reforming reactor 5 through the mixed fluid pipeline 19;
the methanol reforming reactor 5 is connected with the inlet of a first condenser 6 through a first synthetic gas pipeline 20, wherein the first synthetic gas pipeline 20 is connected with the hot side of the first heat exchanger 3, the outlet of the first condenser 6 is connected with the inlet of a pressure swing absorber 7 through a second synthetic gas pipeline 21, and the water outlet of the first condenser 6 is connected with a first water drainage pipeline 22; the hydrogen outlet of the pressure swing absorber 7 is connected with the inlet of the first gas compressor 8 through the front section of the hydrogen conveying pipeline 23, and the outlet of the first gas compressor 8 is connected with the hydrogen inlet of the second mixer 11 through the rear section of the hydrogen conveying pipeline 23;
the air inlet of the air separation device 9 is connected with an air conveying pipeline 24, the nitrogen outlet of the air separation device 9 is connected with the inlet of a second gas compressor 10 through the front section of a nitrogen conveying pipeline 25, the outlet of the second gas compressor 10 is connected with the nitrogen inlet of a second mixer 11 through the rear section of the nitrogen conveying pipeline 25, the outlet of the second mixer 11 is connected with the inlet of a synthetic ammonia reactor 12 through a first mixed gas pipeline 26, the outlet of the synthetic ammonia reactor is connected with the synthetic gas inlet of a methanol reforming reactor through the front section of a third synthetic gas pipeline 27, the synthetic gas outlet of the methanol reforming reactor is connected with the inlet of a rectifying tower 13 through the rear section of the third synthetic gas pipeline 27, and the outlet of the rectifying tower 13 is connected with an ammonia conveying pipeline 28.
The valve gas outlet of the pressure swing adsorber 7 is connected with the valve gas inlet of the third mixer 14 through a valve gas conveying pipeline 29, the oxygen outlet of the air separation device 9 is connected with the oxygen inlet of the third mixer 14 through an oxygen conveying pipeline 30, the outlet of the third mixer 14 is connected with the inlet of the combustion chamber 15 through a second mixed gas pipeline 31, the flue gas outlet of the combustion chamber 15 is connected with the flue gas inlet of the methanol reforming reactor 5 through the front section of a flue gas pipeline 32, the flue gas outlet of the methanol reforming reactor 5 is connected with the inlet of the condenser II 16 through the rear section of the flue gas pipeline 32, the rear section of the flue gas pipeline 32 is connected with the hot side of the second heat exchanger 4, the water outlet of the second condenser 16 is connected with a drainage pipeline II 33, and the carbon dioxide outlet of the second condenser 16 is connected with a carbon dioxide conveying pipeline 34.
Wherein the first mixer 1 is a fluid mixing device for uniformly mixing a certain proportion of methanol and water.
The hydraulic pump 2 is a fluid pressurizing device for lifting a low-pressure fluid into a high-pressure and high-pressure fluid.
The first heat exchanger 3 is used for preheating the mixture of methanol and water, the second heat exchanger 4 is used for secondarily heating the mixture of methanol and water, so that the methanol and water are fully vaporized, the reaction efficiency of hydrogen production by reforming the methanol is improved, on the other hand, the heat source of the second heat exchanger is from high-temperature flue gas generated by valve gas combustion, and the step is used for recycling the waste heat of the high-temperature flue gas, so that the resource utilization efficiency is improved.
The methanol reforming reactor 5 internally carries out a methanol reforming hydrogen production reaction and all other reactions which may occur, and the first synthesis gas obtained by the reforming reaction mainly consists of hydrogen and carbon dioxide.
The pressure swing adsorber 7 is a device for separating the mixed gas to separate hydrogen from the first synthesis gas and provide a hydrogen feed for the subsequent synthesis of ammonia.
The first gas compressor 8 and the second gas compressor 10 are gas pressurizing means for pressurizing hydrogen and nitrogen for the purpose of providing reaction conditions for synthesizing ammonia from hydrogen and nitrogen.
The air separation unit 9 is a device commonly known in the art for separating nitrogen and oxygen from air.
The synthesis ammonia reaction and all other reactions that may occur within the synthesis ammonia reactor 12, with the second synthesis gas resulting from the reaction being predominantly ammonia.
The combustion chamber 15 is a place where the combustion reaction of valve gas and oxygen and other possible reactions occur, and the high-temperature flue gas generated by the combustion is mainly carbon dioxide and water vapor. The device may also be replaced by other devices that provide space for the combustion reaction.
The second mixer 11 and the third mixer 14 are gas mixing means for uniformly mixing two gases into one gas to improve the reaction efficiency.
The specific process flow is as follows:
(1) Methanol and water are fully mixed in a first mixer 1 according to a certain proportion, mixed fluid is pressurized by a hydraulic pump 2, then is preheated by a first heat exchanger 3 and heated by a second heat exchanger 4 in sequence, enters a methanol reforming reactor 5 to generate first synthesis gas through a methanol reforming reaction, the first synthesis gas firstly exchanges heat by the first heat exchanger 3, then enters a first condenser 6, is condensed and then is introduced into a pressure swing adsorber 7, and pure hydrogen is obtained from the first synthesis gas through pressure swing adsorption;
(2) The hydrogen is pressurized by a first gas compressor 8 and then enters a second mixer 11, air is introduced into an air separation device 9 to obtain a pure nitrogen flow, the air flow is pressurized by a second gas compressor 10 and then enters the second mixer 11, the hydrogen and the nitrogen are uniformly mixed in the second mixer 11 to form a first mixed gas, the first mixed gas enters a synthesis ammonia reactor 12 to generate synthesis ammonia reaction to obtain a second synthesis gas, the second synthesis gas provides heat for the methanol reforming reaction by a methanol reforming reactor 5, and then the second synthesis gas enters a rectifying tower 13 to be rectified to obtain pure ammonia;
(3) The valve gas of the pressure swing absorber 7 is introduced into the third mixer 14, pure oxygen obtained by air passing through the air separation device 9 is introduced into the third mixer 14, the valve gas and the oxygen are uniformly mixed in the third mixer 14 to obtain second mixed gas, the second mixed gas is introduced into the combustion chamber 15 to be combusted to generate high-temperature flue gas, the high-temperature flue gas provides heat for the methanol reforming reaction through the methanol reforming reactor 5 and then provides heat for the mixture of methanol and water before entering the methanol reforming reactor through the second heat exchanger 4, and then the high-purity carbon dioxide is obtained by condensation through the second condenser 16, and carbon capture is implemented on the carbon dioxide.
The invention provides a method and a system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming, which realize the root cause of zero-energy-consumption carbon capture as follows: the synthesis gas of the methanol reforming hydrogen production is subjected to pressure swing adsorption to obtain a pure hydrogen stream for generating synthesis ammonia reaction; the main components of the valve gas obtained by pressure swing adsorption are carbon dioxide and a small amount of hydrogen, and the flue gas generated by the combustion of the valve gas and pure oxygen is utilized to drive the reforming reaction of methanol to carry out, and then heat is provided for heating the mixture of methanol and water, so that the heat energy grade of the flue gas is improved to the chemical energy grade of the synthesis gas. The synthesis gas generated in the ammonia synthesis process has higher temperature and can also be used for driving the methanol reforming reaction to be carried out, thereby saving the external energy supply. The flue gas drives a plurality of processes and can obtain high-purity carbon dioxide after condensing and separating water, so that the energy consumption of carbon capture is greatly reduced.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (4)
1. The method for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming is characterized by comprising the following steps of:
s1, mixing methanol and water in a certain proportion, reforming, condensing and pressure swing adsorption to obtain pure hydrogen;
s2, mixing the pressurized pure nitrogen with the pressurized pure hydrogen to perform a synthetic ammonia reaction, and rectifying a synthetic product to obtain pure ammonia;
s3, performing pressure swing adsorption separation in S1 to obtain valve gas which contains carbon dioxide and a small amount of hydrogen as main components, mixing the valve gas with pure oxygen for combustion to generate high-temperature flue gas, condensing the high-temperature flue gas after the high-temperature flue gas provides heat for the reforming reaction in S1 to obtain high-purity carbon dioxide, and capturing carbon;
s1, preheating a mixture of methanol and water by using waste heat of first synthesis gas obtained by reforming;
the second synthesis gas obtained by the synthesis ammonia reaction in S2 provides heat for the reforming reaction in S1;
the high-temperature flue gas burnt by valve gas in S3 provides heat for reforming reaction in S1, and the waste heat provides heat for the mixture of methanol and water before entering the methanol reforming reactor;
the device comprises a first condenser, a first heat exchanger, a second heat exchanger, a methanol reforming reactor, a first condenser, a pressure swing adsorber, a first gas compressor, a second gas compressor, a synthetic ammonia reactor, a rectifying tower, a combustion chamber and a second condenser, wherein the first mixer is provided with a methanol inlet and a water inlet which are respectively connected with a methanol conveying pipeline and a water supply pipeline, the outlet of the first mixer is connected with the cold side inlet of the second heat exchanger and is used for heating a mixture of methanol and water, the cold side outlet of the second heat exchanger is connected with the inlet of the methanol reforming reactor, so that the methanol and water undergo reforming reaction in the methanol reforming reactor to generate first synthetic gas, the outlet of the methanol reforming reactor is connected with the inlet of the first condenser, the outlet of the first condenser is connected with the inlet of the pressure swing adsorber, the first synthetic gas is subjected to pressure swing adsorption to obtain pure hydrogen, and the outlet of the pressure swing adsorber is connected with the inlet of the first gas compressor; the inlet of the second gas compressor is connected with a nitrogen source, the synthetic ammonia reactor is respectively connected with the outlet of the first gas compressor and the outlet of the second gas compressor, the synthetic ammonia reaction is carried out in the synthetic ammonia reactor to obtain second synthetic gas, the outlet of the synthetic ammonia reactor is connected with the inlet of the rectifying tower, and the second synthetic gas is rectified to obtain pure ammonia gas;
the combustion chamber is respectively connected with a valve gas outlet of the pressure swing adsorber and an oxygen source, a flue gas outlet of the combustion chamber is connected with the methanol reforming reactor, high-temperature flue gas generated by combustion provides a heat source for reforming reaction, the flue gas after heat exchange is condensed by the second condenser to obtain high-purity carbon dioxide, and carbon capture is carried out on the carbon dioxide; the first heat exchanger is connected with the second heat exchanger through a mixed fluid pipeline, and the mixed fluid pipeline is connected with the cold side of the first heat exchanger, so that the first heat exchanger preheats the mixture of methanol and water; the methanol reforming reactor is connected with the first condenser through a first synthesis gas pipeline, and the first synthesis gas pipeline is connected with the hot side of the first heat exchanger and used as a heat source of the first heat exchanger; the device also comprises a second mixer and a third mixer, wherein the second mixer is provided with a hydrogen inlet and a nitrogen inlet, and is respectively connected with the outlet of the first gas compressor and the outlet of the second gas compressor, and the outlet of the second mixer is connected with the mixed gas inlet of the synthetic ammonia reactor; the third mixer is provided with a valve gas inlet and an oxygen inlet which are respectively connected with a valve gas outlet and an oxygen source of the pressure swing adsorber, and an outlet of the third mixer is connected with an inlet of the combustion chamber.
2. The method for preparing ammonia based on zero-energy carbon capture methanol reforming of claim 1, wherein the method comprises the following steps: the synthetic ammonia reactor is connected with the rectifying tower through a third synthetic gas pipeline, and the third synthetic gas pipeline is connected with the methanol reforming reactor to provide a heat source for reforming reaction.
3. The method for preparing ammonia based on zero-energy carbon capture methanol reforming of claim 1, wherein the method comprises the following steps: the flue gas outlet of the combustion chamber is connected with the flue gas inlet of the methanol reforming reactor through the front section of the flue gas pipeline, and the flue gas outlet of the methanol reforming reactor is connected with the inlet of the second condenser through the rear section of the flue gas pipeline, wherein the rear section of the flue gas pipeline is connected with the hot side of the second heat exchanger.
4. The method for preparing ammonia based on zero-energy carbon capture methanol reforming of claim 1, wherein the method comprises the following steps: the nitrogen source and the oxygen source are both from the same air separation device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210500804.2A CN114804025B (en) | 2022-05-10 | 2022-05-10 | Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210500804.2A CN114804025B (en) | 2022-05-10 | 2022-05-10 | Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114804025A CN114804025A (en) | 2022-07-29 |
| CN114804025B true CN114804025B (en) | 2024-04-05 |
Family
ID=82513261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210500804.2A Active CN114804025B (en) | 2022-05-10 | 2022-05-10 | Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114804025B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117819479B (en) * | 2023-12-29 | 2024-07-12 | 中海石油气电集团有限责任公司 | System for preparing synthesis gas by natural gas hydrogen production coupled with carbon dioxide trapping |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211880A (en) * | 1990-12-21 | 1993-05-18 | Haldor Topsoe A/S | Process for the preparation of ammonia synthesis gas |
| CN101708821A (en) * | 2009-12-08 | 2010-05-19 | 四川亚联高科技股份有限公司 | Methanol steam hydrogen production technology by using catalytic combustion flue gas as heat source |
| CN104773708A (en) * | 2015-04-16 | 2015-07-15 | 广东合即得能源科技有限公司 | Hydrogen raw material production equipment and process for ammonia synthesis |
| CN106784939A (en) * | 2016-12-30 | 2017-05-31 | 广东能态科技投资有限公司 | A kind of methanol-water reformation hydrogen production generator |
| CN112901322A (en) * | 2021-01-15 | 2021-06-04 | 集美大学 | Diesel engine waste gas waste heat recycling system based on methanol steam reforming hydrogen production |
| CN113446137A (en) * | 2021-07-21 | 2021-09-28 | 大连理工大学 | Hydrogen-ammonia dual-fuel engine system for catalytically reforming methanol to supply hydrogen by waste gas waste heat |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10116152A1 (en) * | 2001-03-31 | 2002-10-10 | Mg Technologies Ag | Process for the production of ammonia from methanol |
-
2022
- 2022-05-10 CN CN202210500804.2A patent/CN114804025B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5211880A (en) * | 1990-12-21 | 1993-05-18 | Haldor Topsoe A/S | Process for the preparation of ammonia synthesis gas |
| CN101708821A (en) * | 2009-12-08 | 2010-05-19 | 四川亚联高科技股份有限公司 | Methanol steam hydrogen production technology by using catalytic combustion flue gas as heat source |
| CN104773708A (en) * | 2015-04-16 | 2015-07-15 | 广东合即得能源科技有限公司 | Hydrogen raw material production equipment and process for ammonia synthesis |
| CN106784939A (en) * | 2016-12-30 | 2017-05-31 | 广东能态科技投资有限公司 | A kind of methanol-water reformation hydrogen production generator |
| CN112901322A (en) * | 2021-01-15 | 2021-06-04 | 集美大学 | Diesel engine waste gas waste heat recycling system based on methanol steam reforming hydrogen production |
| CN113446137A (en) * | 2021-07-21 | 2021-09-28 | 大连理工大学 | Hydrogen-ammonia dual-fuel engine system for catalytically reforming methanol to supply hydrogen by waste gas waste heat |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114804025A (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106185984B (en) | System for jointly producing ammonia and nitric acid based on steam electrolysis method | |
| CN101540410B (en) | Natural gas hydrogen production and proton-exchange film fuel cell integrated generation method and device thereof | |
| CN114804025B (en) | Method and system for preparing ammonia based on zero-energy-consumption carbon capture methanol reforming | |
| CN101993730B (en) | Multifunctional energy system based on appropriate conversion of chemical energy of fossil fuel | |
| CN1869165B (en) | Bifuel reforming multifunctional energy system and its method | |
| CN101704714B (en) | Method for preparing synthesis gas after pure oxygen catalytic partial oxidation of purge gas in methanol synthesis loop to increase yield of methanol, and device | |
| WO2022242598A1 (en) | Apparatus and method for preparing hydrogen-containing product from natural gas on basis of new energy consumption | |
| CN111591957B (en) | Coal bed gas combined cycle power generation and CO2Trapping system and method | |
| CN114988364B (en) | Power generation system based on natural gas hydrogen production and fuel cell technology | |
| CN116283490A (en) | CO is realized to garbage power generation and photovoltaic power generation gas production coupling 2 Method and apparatus for recovering and producing methanol | |
| CN201485400U (en) | Device for preparing synthesis gas after partial oxidation of purge gas in methanol synthesis loop through pure oxygen catalysis to increase methanol in yield | |
| CN101704715B (en) | Method for preparing synthesis gas after pure oxygen non-catalytic partial oxidation of purge gas in methanol synthesis loop to increase yield of methanol, and device therefor | |
| CN101993748B (en) | Method for preparing and synthesizing natural gas by utilizing straw gas | |
| RU2587736C1 (en) | Plant for utilisation of low-pressure natural and associated oil gases and method for use thereof | |
| CN114893264A (en) | Combining hydrogen green with CO 2 Coal-fired oxygen-enriched combustion power generation system and method for resource utilization | |
| CN114522518A (en) | Carbon-containing recycling gas power plant low-cost carbon emission reduction system and method | |
| CN211078472U (en) | Device for improving sulfur recovery efficiency | |
| CN221413049U (en) | System for utilize hydrogen shaft furnace tail gas synthesis methyl alcohol | |
| CN221296785U (en) | Coke oven heating system adopting oxygen-enriched combustion | |
| JP6906087B2 (en) | Hydrogen production system and method by coke in thermal power plant | |
| CN219621111U (en) | CO is realized to garbage power generation and photovoltaic power generation gas production coupling 2 Device for recovering and producing methanol | |
| WO2023155417A1 (en) | Steel process co2 conversion and cyclic utilization method and system | |
| CN213326722U (en) | Natural gas hydrogen production steam generation system | |
| CN201485401U (en) | Device for preparing synthesis gas after partial oxidation of purge gas in methanol synthesis loop through pure oxygen non-catalysis to increase methanol in yield | |
| RU2445262C1 (en) | Method of producing ammonia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |