CN115849400A - Ammonia synthesis process using mixed gas as raw material - Google Patents
Ammonia synthesis process using mixed gas as raw material Download PDFInfo
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- CN115849400A CN115849400A CN202211695593.9A CN202211695593A CN115849400A CN 115849400 A CN115849400 A CN 115849400A CN 202211695593 A CN202211695593 A CN 202211695593A CN 115849400 A CN115849400 A CN 115849400A
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- methanol
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 111
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 76
- 239000002994 raw material Substances 0.000 title claims abstract description 51
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 47
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 336
- 239000007789 gas Substances 0.000 claims abstract description 130
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 239000003245 coal Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000003345 natural gas Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 238000005261 decarburization Methods 0.000 claims abstract description 7
- 230000009466 transformation Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 5
- 230000023556 desulfurization Effects 0.000 claims abstract description 5
- 238000002309 gasification Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003034 coal gas Substances 0.000 description 8
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
A synthesis ammonia process using mixed gas as raw material relates to the technical field of synthesis ammonia process, and the process comprises the following steps: the method comprises a methanol process and a synthetic ammonia process, wherein the methanol process takes coal as a raw material, and the coal is prepared into methanol through the processes of coal water slurry preparation, gasification, transformation, low-temperature methanol washing and methanol synthesis; the synthetic ammonia process takes acetylene tail gas prepared by cracking natural gas as a raw material, the acetylene tail gas is compressed and then subjected to desulfurization, hydrogenation, medium-low temperature conversion, decarburization and pressure swing adsorption to prepare high-purity hydrogen, the high-purity hydrogen and pure nitrogen are subjected to methanation and synthesis to prepare liquid ammonia, and the hydrogenation comprises first-stage hydrogenation and second-stage hydrogenation; the methanol process obtains methanol purified gas after a low-temperature methanol washing process, and the methanol purified gas is merged into a first-stage hydrogenation inlet of the synthetic ammonia process through a pipeline. The invention has the beneficial effects that: the methanol process and the ammonia synthesis process can be effectively combined, the consumption of liquid ammonia products per ton of ammonia raw material gas can be greatly reduced, and the productivity is improved.
Description
Technical Field
The invention relates to the technical field of ammonia synthesis processes, in particular to an ammonia synthesis process taking mixed gas as a raw material.
Background
In the chemical industry, the raw material of the synthetic ammonia process is coal or natural gas, the synthetic gas is prepared by coal gasification or natural gas conversion, and the synthetic gas is purified and synthesized to prepare ammonia. In the joint production of synthetic ammonia and methanol, synthetic ammonia is generally adopted to co-produce methanol, and a part of process gas is separated from a transformation process of a synthetic ammonia process and used as methanol synthesis gas to produce methanol, so that the transformation gas not only needs to meet the process requirements of synthetic ammonia, but also needs to meet the process requirements of methanol, and therefore, the operation difficulty of the transformation process is high, the equipment investment is high, and a synthetic ammonia process system and a methanol process system have serious mutual influence; and the traditional ammonia synthesis process and the methanol process have single raw material, generally coal or natural gas is used as the raw material, the byproduct tail gas generated in acetylene preparation by natural gas cracking is used as the raw material to prepare ammonia, the raw material gas of the liquid ammonia product has high consumption of each ton of ammonia of acetylene tail gas, and the consumption is generally as follows: 2350-2395NM 3/ton ammonia.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a process for synthesizing ammonia by taking mixed gas as a raw material, which aims to solve the technical problems.
The invention provides a process for synthesizing ammonia by taking mixed gas as a raw material, which comprises the following steps: the method comprises a methanol process and a synthetic ammonia process, wherein the methanol process takes coal as a raw material, and the coal is prepared into methanol through the processes of coal water slurry preparation, gasification, transformation, low-temperature methanol washing and methanol synthesis; the ammonia synthesis process takes acetylene tail gas prepared by natural gas cracking as a raw material, the acetylene tail gas is compressed and then subjected to desulfurization, hydrogenation, medium-low temperature conversion, decarburization and pressure swing adsorption to prepare high-purity hydrogen, the high-purity hydrogen and pure nitrogen are subjected to methanation and synthesis to prepare liquid ammonia, and the hydrogenation comprises first-stage hydrogenation and second-stage hydrogenation; the methanol process obtains methanol purified gas after a low-temperature methanol washing process, and the methanol purified gas is merged into a first-stage hydrogenation inlet of the synthetic ammonia process through a pipeline.
Therefore, the liquid ammonia can be produced by taking the mixed gas of the acetylene tail gas and the methanol purified gas in any proportion as a raw material, and the liquid ammonia can also be produced by independently using the acetylene tail gas or the methanol purified gas.
The pipeline of the methanol purified gas is provided with a flowmeter, a separator, an emptying valve, a cut-off valve, a pressure regulating valve, a manual gate valve, a check valve and a heater, the separator is arranged behind the flowmeter, and the separator separates liquid carried in the methanol purified gas; an air release valve is arranged behind the separator and used for releasing pressure of a methanol purification gas pipeline; a stop valve is arranged behind the emptying valve and used for cutting off the synthetic ammonia raw material; a pressure regulating valve is arranged behind the cut-off valve and can control the pressure of the methanol purification gas so as to meet the technological requirements of the synthesis ammonia; a manual valve is arranged behind the pressure regulating valve, a check valve is arranged behind the manual valve, and the check valve is used for preventing acetylene tail gas from flowing back to the methanol gas pipeline after the pressure of the methanol gas pipeline is relieved;
the heater is arranged behind the check valve on the methanol purification gas pipe line and used for improving the temperature of the methanol purification gas and meeting the process requirement of the synthesis ammonia.
The pressure swing adsorption process of the ammonia synthesis process is provided with a bypass pipeline, and the pressure swing adsorption process of the ammonia synthesis process mainly aims at removing CH in purified gas in an upstream decarburization process 4 And small amount of CO and CO 2 、C 2 H 6 、H 2 O、N 2 When the raw material of the ammonia synthesis process is methanol purified gas, H in the purified gas in the decarbonization process 2 The content is as high as more than 98.5 percent, and because the content of methane in the methanol purified gas is low, the synthetic ammonia process can stride over the pressure swing adsorption process, the purified gas of the decarbonization process of the synthetic ammonia process is directly sent to the methanation process through a newly added bypass pipeline, and the energy consumption of the synthetic ammonia can be greatly reduced.
The methanol purification gas obtained after the low-temperature methanol washing process of the methanol process comprises the following components: h 2 :66.29％、CO:30.71％、CO 2 :2.50％、CH 4 :0.03％、N 2 0.14 percent and Ar 0.32 percent. The pressure of the methanol purification gas after the low-temperature methanol washing procedure of the coal gas methanol technology is 4.6-5.4MPa.G, and the temperature is 0-30 ℃;
the acetylene tail gas prepared by natural gas cracking comprises the following components: h 2 :62.569％、CO:30.156％、CO 2 :3.57％、CH 4 :2.67％、N 2 :0.13％、Ar:0.104％、O 2 :0.204％、H 2 O:0.34％、C 2 H 4 :0.217％、C 2 H 2 :0.018％；
The acetylene tail gas component is similar to the methanol purified gas component, the methanol purified gas pressure meets the requirements of the synthesis ammonia process, the methanol purified gas temperature is lower, and a part of the methanol purified gas after the temperature is increased is merged into a first-section hydrogenation inlet of the synthesis ammonia process, so that the liquid ammonia can be produced by using the mixed gas of the acetylene tail gas and the methanol purified gas in any proportion as raw materials, and the liquid ammonia can also be produced by using the acetylene tail gas or the methanol purified gas alone; according to the operation condition of the upstream raw material device for synthesizing ammonia, raw materials can be switched at any time to produce liquid ammonia, the operation flexibility of the device is improved, and the acetylene tail gas ammonia synthesis process system and the coal gas methanol process system are not affected by each other.
The invention has the beneficial effects that:
1. the mixed gas of acetylene tail gas and coal gas methanol purified gas is used as a raw material to produce liquid ammonia, so that a methanol process and an ammonia synthesis process can be effectively combined, the consumption of liquid ammonia products per ton of ammonia raw material gas can be greatly reduced, and the productivity is improved;
2. according to the price of coal or natural gas raw materials, more economic raw materials can be selected to produce liquid ammonia, the production cost is reduced, and the economic benefit is maximized;
3. the device has high operation flexibility, two raw materials of acetylene tail gas and methanol purified gas can be prepared in any proportion, and when one raw material is interrupted in production, the device cannot be stopped due to the interruption of the raw material, so that the continuous operation period of the device is prolonged;
4. when the synthetic ammonia process uses the methanol purified gas as the raw material, the pressure swing adsorption process of a local unit can be selected and stopped, and the energy consumption of the synthetic ammonia is greatly reduced.
Drawings
FIG. 1 is a process flow diagram of the present invention;
in the figure: 1. methanol process, 2, ammonia synthesis process, 3, methanol purified gas, 4, flowmeter, 5, separator, 6, blow-down valve, 7, cut-off valve, 8, pressure regulating valve, 9, manual gate valve, 10, check valve, 11 and heater.
Detailed Description
Example 1
As shown in fig. 1, the present invention provides a process 2 for synthesizing ammonia by using a gas mixture as a raw material, which comprises the following steps: the method comprises a methanol process 1 and an ammonia synthesis process 2, wherein the methanol process 1 takes coal as a raw material, and the coal is prepared into methanol through the working procedures of coal water slurry preparation, gasification, transformation, low-temperature methanol washing and methanol synthesis; the synthetic ammonia process 2 takes acetylene tail gas prepared by natural gas cracking as a raw material, the acetylene tail gas is compressed and then subjected to desulfurization, hydrogenation, medium-low temperature conversion, decarburization and pressure swing adsorption to prepare high-purity hydrogen, the high-purity hydrogen and pure nitrogen are subjected to methanation and synthesis to prepare liquid ammonia, and the hydrogenation comprises first-stage hydrogenation and second-stage hydrogenation; obtaining a methanol purified gas 3 after a low-temperature methanol washing procedure of the methanol process 1, wherein the methanol purified gas 3 is merged into a first-stage hydrogenation inlet of the ammonia synthesis process 2 through a pipeline; the liquid ammonia can be produced by using the mixed gas of acetylene tail gas and methanol purified gas 3 in any proportion as raw materials, or by using the acetylene tail gas or the methanol purified gas 3 alone;
a flow meter 4, a separator 5, an emptying valve 6, a cut-off valve 7, a pressure regulating valve 8, a manual gate valve 9, a check valve 10 and a heater are arranged on a pipeline of the methanol purified gas 3, the separator 5 is arranged behind the flow meter 4, and the separator 5 separates liquid carried in the methanol purified gas 3; an emptying valve 6 and a cut-off valve 7 are arranged behind the separator 5, and the emptying valve 6 is used for the pipeline pressure relief of the methanol purified gas 3; the shut-off valve 7 is used for shutting off the synthetic ammonia raw material; a pressure regulating valve 8 is arranged behind the cut-off valve 7, and the pressure regulating valve 8 can control the pressure of the methanol purified gas 3 so as to meet the requirement of the synthesis ammonia process 2; a manual valve 9 is arranged behind the pressure regulating valve 8, a check valve 10 is arranged behind the manual valve 9, and the check valve 10 is used for preventing acetylene tail gas from flowing back to the methanol gas pipeline after the methanol gas pipeline is decompressed;
a heater is arranged on the pipeline of the methanol purified gas 3 after the upper stop return valve 10, and the heater is used for increasing the temperature of the methanol purified gas 3 and meeting the requirements of the synthesis ammonia process 2;
the pressure swing adsorption process of the ammonia synthesis process 2 is provided with a bypass pipeline, and the pressure swing adsorption process of the ammonia synthesis process 2 mainly aims at removing CH in purified gas in an upstream decarburization process 4 And small amount of CO and CO 2 、C 2 H 6 、H 2 O、N 2 When the raw material of the ammonia synthesis process 2 is the methanol purified gas 3, H in the purified gas of the decarburization process 2 The content is as high as more than 98.5 percent, and because the content of methane in the methanol purified gas 3 is low, the synthetic ammonia process 2 can stride over the pressure swing adsorption process, and the purified gas of the decarbonization process of the synthetic ammonia process 2 is directly sent to the methanation process through a newly added bypass pipeline, so that the energy consumption of the synthetic ammonia can be greatly reduced;
the methanol purified gas 3 obtained after the low-temperature methanol washing process of the methanol process 1 comprises the following components: h 2 :66.29％、CO:30.71％、CO 2 :2.50％、CH 4 :0.03％、N 2 0.14 percent and Ar 0.32 percent. The pressure of methanol purified gas 3 after the low-temperature methanol washing procedure of the coal gas methanol process 1 is 4.6-5.4MPa.G, and the temperature is 0-30 ℃;
the acetylene tail gas prepared by natural gas cracking comprises the following components: h 2 :62.569％、CO:30.156％、CO 2 :3.57％、CH 4 :2.67％、N 2 :0.13％、Ar:0.104％、O 2 :0.204％、H 2 O:0.34％、C 2 H 4 :0.217％、C 2 H 2 :0.018％；
The acetylene tail gas component is similar to the methanol purified gas 3 component, and the pressure of the methanol purified gas 3 meets the requirement of the synthesis ammonia process 2, but the temperature of the methanol purified gas 3 is lower, and a part of the methanol purified gas 3 after the temperature is increased is merged into a first-section hydrogenation inlet of the synthesis ammonia process 2, so that the liquid ammonia can be produced by using the mixed gas of the acetylene tail gas and the methanol purified gas 3 in any proportion as raw materials, and the liquid ammonia can also be produced by using the acetylene tail gas or the methanol purified gas 3 alone; according to the operation condition of an upstream raw material device for synthesizing ammonia, raw materials can be switched at any time to produce liquid ammonia, the operation flexibility of the device is improved, and a system of an acetylene tail gas ammonia synthesis process 2 and a system of a coal gas methanol process 1 are not affected by each other;
specifically, when the methanol purified gas 3 is used as the raw material to produce the liquid ammonia, the raw material gas compressor of the ammonia synthesis process 2 needs to be shut down, the inlet of the desulfurization tank is closed, the methanol purified gas 3 is prevented from flowing back to the raw material gas compressor, and the overpressure of the low pressure cylinder of the raw material gas compressor is prevented; the inlet temperature of the first-stage hydrogenation of the ammonia synthesis process 2 is low, and a methanol purification gas 3 heater is used to ensure the inlet temperature of the first-stage hydrogenation.
Synthesis of Ammonia Process 2 from mixture of acetylene Tail gas and methanol purified gas 3, pressure swing adsorption of H in byproduct Tail gas 2 When the content is increased, a proper amount of low-pressure nitrogen is required to be added into the byproduct tail gas of pressure swing adsorption, so that the safety risk is reduced.
Claims (6)
1. A process for synthesizing ammonia by taking mixed gas as a raw material is characterized by comprising the following steps: the method comprises a methanol process and a synthetic ammonia process, wherein the methanol process takes coal as a raw material, and the coal is prepared into methanol through the processes of coal water slurry preparation, gasification, transformation, low-temperature methanol washing and methanol synthesis; the synthetic ammonia process takes acetylene tail gas prepared by cracking natural gas as a raw material, the acetylene tail gas is compressed and then subjected to desulfurization, hydrogenation, medium-low temperature conversion, decarburization and pressure swing adsorption to prepare high-purity hydrogen, the high-purity hydrogen and pure nitrogen are subjected to methanation and synthesis to prepare liquid ammonia, and the hydrogenation comprises first-stage hydrogenation and second-stage hydrogenation; the methanol process obtains methanol purified gas after a low-temperature methanol washing process, and the methanol purified gas is merged into a first-stage hydrogenation inlet of the synthetic ammonia process through a pipeline.
2. The ammonia synthesis process using the gas mixture as the raw material according to claim 1, which is characterized in that: the pipeline of the methanol purified gas is provided with a flowmeter, a separator, an emptying valve, a cut-off valve, a pressure regulating valve, a manual gate valve, a check valve and a heater, the separator is arranged behind the flowmeter, the emptying valve and the cut-off valve are arranged behind the separator, a pressure regulating valve is arranged behind the cut-off valve, the manual valve is arranged behind the pressure regulating valve, and the check valve is arranged behind the manual valve; and a heater is arranged behind the check valve on the methanol purification gas pipeline.
3. The ammonia synthesis process using the gas mixture as the raw material according to claim 1, which is characterized in that: the pressure swing adsorption process of the ammonia synthesis process is provided with a bypass pipeline.
4. The ammonia synthesis process using the gas mixture as the raw material according to claim 1, which is characterized in that: the components of the methanol purified gas obtained after the low-temperature methanol washing process of the methanol process are as follows: h 2 :66.29％、CO:30.71％、CO 2 :2.50％、CH 4 :0.03％、N 2 :0.14％、Ar:0.32％。
5. The process of claim 4, wherein the ammonia synthesis process is characterized in that: the acetylene tail gas prepared by natural gas cracking comprises the following components: h 2 :62.569％、CO:30.156％、CO 2 :3.57％、CH 4 :2.67％、N 2 :0.13％、Ar:0.104％、O 2 :0.204％、H 2 O:0.34％、C 2 H 4 :0.217％、C 2 H 2 :0.018％。
6. The ammonia synthesis process using the gas mixture as the raw material according to claim 5, characterized in that: the acetylene gas component and the methanol purified gas component are similar, the methanol purified gas temperature is increased and then is merged into a section of hydrogenation inlet of the synthetic ammonia process, and the mixed gas of the acetylene gas and the methanol purified gas is used as a raw material to produce liquid ammonia.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014127913A2 (en) * | 2013-02-21 | 2014-08-28 | Faramarz Bairamijamal | High pressure process for co2 capture, utilization for heat recovery, power cycle, super-efficient hydrogen based fossil power generation and conversion of liquid co2 with water to syngas and oxygen |
| CN106672898A (en) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material |
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- 2022-12-28 CN CN202211695593.9A patent/CN115849400B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014127913A2 (en) * | 2013-02-21 | 2014-08-28 | Faramarz Bairamijamal | High pressure process for co2 capture, utilization for heat recovery, power cycle, super-efficient hydrogen based fossil power generation and conversion of liquid co2 with water to syngas and oxygen |
| CN106672898A (en) * | 2017-01-17 | 2017-05-17 | 青海盐湖工业股份有限公司 | Method for synthesizing ammonia by taking byproduct tail gas in process of producing acetylene by pyrolyzing natural gas as raw material |
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