CN110902653A - Method for switching raw material crude CO into synthesis gas by synthesis gas separation device without stopping - Google Patents
Method for switching raw material crude CO into synthesis gas by synthesis gas separation device without stopping Download PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 100
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 87
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 87
- 238000000926 separation method Methods 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 227
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000001257 hydrogen Substances 0.000 claims abstract description 110
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 110
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 54
- 230000001105 regulatory effect Effects 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 51
- 238000003795 desorption Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- 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
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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- 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
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- 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
- C01B32/40—Carbon monoxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0009—Physical processing
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Abstract
The invention relates to a method for switching raw material crude CO into synthesis gas by a synthesis gas separation device without stopping, which ensures that a system keeps stable operation in the process of converting gas in a raw material pipeline from crude carbon monoxide into synthesis gas by regulating the amount of CO products in a CO circulation pipeline returning to the raw material pipeline and the amount of hydrogen in a hydrogen circulation pipeline returning to the raw material pipeline, and ensures that the product CO supplied by a CO product pipeline keeps a qualified and stable supply state. According to the invention, the return CO amount and the H2 amount of the system are regulated, so that the device can keep stable operation in the process of converting the fed material from crude carbon monoxide into the synthesis gas, and the product CO keeps a qualified and stable supply state, thereby saving the time and cost for stopping and starting compared with the traditional method. Compared with the prior art, the method of the invention saves the time and cost for stopping and driving compared with the traditional method.
Description
Technical Field
The invention belongs to the technical field of industrial gas purification, and particularly relates to a method for switching raw material crude CO into synthesis gas without stopping a synthesis gas separation device.
Background
The CO content of the crude carbon monoxide (RCO for short) produced in industry is only 98 percent, and the impurity H2The content of the carbon monoxide can reach 1 percent, and the purity requirement (generally required CO) of carbon monoxide products in most chemical industries can not be met>98.9％，H2<100ppm)。
Chinese patent CN109437200A discloses a device and a process method for purifying crude carbon monoxide, which utilize crude carbon monoxide (RCO) to produce refined carbon monoxide (PCO), and comprises a temperature swing adsorption unit (1) and a cold box (2) which are connected in sequence, wherein the outlet of the cold box (2) is respectively connected with a CO compressor (3), the pressure swing adsorption unit (4) and a desorption gas compressor (5), the outlet of the pressure swing adsorption unit (4) is connected with a hydrogen product pipeline (9), a CO product pipeline (7) leads out a CO circulation pipeline (8) and is connected with the desorption gas compressor (5), and a hydrogen circulation pipeline (10) is led out between the cold box (2) and the pressure swing adsorption unit (4) and is connected with the desorption gas compressor (5).
The device of above-mentioned patent utilizes the surplus ability of current CO compressor among the synthetic gas separator and desorption gas compressor, purifies RCO into PCO, and the device is simple, and the flow is convenient, and the separation effect is good. However, the above patent only uses a synthesis gas separation device to perform the crude carbon monoxide purification, and the main purpose of the synthesis gas separation device is still to separate the synthesis gas, so when the device of the above patent does not perform the crude carbon monoxide purification but the raw material is replaced by the crude carbon monoxide, the conventional method is to stop the whole device, then replace the gas in the device with nitrogen, finally introduce the synthesis gas, and separate the synthesis gas by the synthesis gas separation device. This is time and labor consuming and costly.
Disclosure of Invention
The invention aims to provide a method for switching raw material crude CO into synthesis gas without stopping a synthesis gas separation device.
The invention improves a device for purifying crude carbon monoxide disclosed in patent CN109437200A, thereby realizing the non-stop switching of the feeding of the crude carbon monoxide (RCO for short) to the feeding of synthesis gas.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a method for switching raw material crude CO into synthesis gas without stopping a synthesis gas separation device, which is carried out based on a system for switching the raw material crude CO into the synthesis gas without stopping the synthesis gas separation device,
the system for switching raw material crude CO into synthetic gas by the synthetic gas separation device without stopping comprises the synthetic gas separation device, wherein the synthetic gas separation device comprises a temperature swing adsorption unit, a cold box, a CO compressor, a pressure swing adsorption unit and a desorption gas compressor, an inlet of the temperature swing adsorption unit is connected with a raw material pipeline, the raw material pipeline is used for accessing crude carbon monoxide or synthetic gas, an outlet of the temperature swing adsorption unit is connected with an inlet of the cold box, one outlet of the cold box is connected with an inlet of the CO compressor, the CO compressor is provided with two outlets, one outlet is connected with a CO product pipeline, and the other outlet is connected back to the cold box, so that circulation is formed between the cold box and the CO compressor,
the other outlet of the cold box is sequentially connected with a pressure swing adsorption unit and a desorption gas compressor,
the outlet of the desorption gas compressor is connected with the inlet of the temperature swing adsorption unit to form circulation, the pressure swing adsorption unit is also provided with another outlet connected with a hydrogen product pipeline,
a CO circulation pipeline is led out from the CO product pipeline and connected with a raw material pipeline, a hydrogen circulation pipeline is led out from the hydrogen product pipeline and connected with the raw material pipeline,
the outlet of the cold box is also provided with a tail gas discharge pipeline, a tail gas circulation pipeline is led out of the tail gas discharge pipeline, and the tail gas circulation pipeline is connected with a raw material pipeline;
the raw material pipeline is also connected with a hydrogen supplementing pipeline;
the method comprises the following steps: by adjusting the amount of the CO product in the CO circulating pipeline returning to the raw material pipeline and the amount of the hydrogen in the hydrogen circulating pipeline returning to the raw material pipeline, the system can keep stable operation in the process of converting the gas in the raw material pipeline from the crude carbon monoxide into the synthetic gas, and the product CO supplied by the CO product pipeline can keep a qualified and stable supply state.
Further, the content of the components in the crude carbon monoxide is as follows: h20-1％，CH40-1％，N2+ Ar 0-0.5%, and the balance CO.
Further, the content of the components in the synthesis gas is as follows: CO content 40-60%, N2+Ar 0-0.2％，CH40-1% of the total weight of the composition, and the balance of the composition is H2。
Further, in the process of converting the gas in the raw material line from crude carbon monoxide to synthesis gas, the following method is adopted:
A. maintaining the load of the synthesis gas separation device at 50% of the designed feeding amount, slowly injecting the raw synthesis gas into the raw material pipeline, and simultaneously slowly reducing the injection amount of the crude carbon monoxide;
B. stopping hydrogen injection after the hydrogen content in the feed line exceeds 2%;
C. starting the synthesis gas separation device, keeping a full-circulation state, compressing the circulating tail gas in the tail gas circulating pipeline by a circulating gas compressor, and returning the compressed circulating tail gas to the raw material pipeline;
D. continuously increasing the flow of the raw material synthesis gas and reducing the flow of the crude carbon monoxide, and gradually adjusting the amount of the CO product in the CO circulating pipeline returning to the raw material pipeline, the amount of the hydrogen in the hydrogen circulating pipeline returning to the raw material pipeline, and the amount of the circulating tail gas in the tail gas circulating pipeline returning to the raw material pipeline;
E. when the feeding amount of the synthesis gas reaches 50% of the designed maximum feeding amount, the amount of the CO product in the CO circulating pipeline returning to the raw material pipeline, the amount of the hydrogen in the hydrogen circulating pipeline returning to the raw material pipeline, and the amount of the circulating tail gas in the tail gas circulating pipeline returning to the raw material pipeline reach the designed values, at the moment, the raw material synthesis gas completely replaces the crude carbon monoxide, and the device is operated in a synthesis gas separation mode.
Further, in step a, the syngas flow rate is increased at a rate not exceeding 0.5% per minute and the crude carbon monoxide flow rate is decreased at a rate not exceeding 0.25% per minute of the designed maximum feed rate. The flow rates of the syngas increase and crude carbon monoxide decrease were maintained at about 2:1 to ensure that the flow rate of the CO component in the feed remained essentially constant.
Further, in step B, the hydrogen content in the feed line is calculated based on the composition of the crude carbon monoxide, the composition of the syngas, and on the amount of CO product returned to the feed line in the CO recycle line, and the amount of hydrogen returned to the feed line in the hydrogen recycle line, and the amount of hydrogen in the hydrogen make-up line.
Further, in the step B, after the hydrogen content in the raw material line exceeds 2%, the hydrogen circulation line and the hydrogen replenishment line are stopped from injecting hydrogen into the raw material line.
Further, when the system for switching raw material crude CO into synthesis gas is used by the synthesis gas separation device without stopping the system, and crude carbon monoxide is introduced into a raw material pipeline, the operation method for purifying the crude carbon monoxide comprises the following steps:
a. the crude carbon monoxide raw material enters a temperature swing adsorption unit to remove carbon dioxide and water, and then enters a cold box to be dried and separated to form three strands of materials, namely CO and crude H2And contain CH4The tail gas of (2);
b. coarse H2The hydrogen treated by the pressure swing adsorption unit is led out from a hydrogen product pipeline, desorbed gas from the pressure swing adsorption unit also enters a desorbed gas compressor, and gas discharged by the desorbed gas compressor enters the temperature swing adsorption unit again to form circulation;
c. CO enters a CO compressor, and the discharged CO is taken as a product to be delivered;
d. containing CH4The tail gas is directly discharged.
Further, a hydrogen regulating valve for regulating the hydrogen flow is arranged on the hydrogen replenishing pipeline; and a CO product regulating valve is arranged on the CO product pipeline, and the CO circulating pipeline is arranged in front of the CO product regulating valve according to the gas flow direction in the CO product pipeline.
Further, a CO circulation regulating valve is arranged on the CO circulation pipeline; a hydrogen circulation regulating valve for regulating the flow rate of circulating hydrogen is arranged on the hydrogen circulation pipeline;
and a tail gas regulating valve is arranged on the tail gas discharge pipeline, and the tail gas circulation pipeline is arranged in front of the tail gas regulating valve according to the flow direction of tail gas in the tail gas discharge pipeline.
Further, a tail gas circulation regulating valve is arranged on the tail gas circulation pipeline.
Further, the temperature swing adsorption unit, the pressure swing adsorption unit and the cold box are all conventional device structures for industrial gas purification, and a person skilled in the art can select from the conventional temperature swing adsorption unit, the pressure swing adsorption unit and the cold box.
The improvement of the invention is that: the original synthesis gas separation device is additionally provided with: 1) the CO product returns to a CO circulating pipeline and a regulating valve of the raw material pipeline; 2) h2The product returns to the hydrogen circulation pipeline and the regulating valve of the raw material pipeline; 3) a tail gas circulation pipeline is led out of the tail gas discharge pipeline and is connected with the raw material pipeline; 4) for compensating H in the apparatus2Loss and increase of hydrogen supply lines.
The method of the invention utilizes the surplus compression capacity of the existing CO compressor and desorption gas compressor in the synthesis gas device to mix CO products and H2The product is recycled to the raw material, thereby realizing the further purification of RCO into PCO by utilizing a synthesis gas separation device. When the device is used as a synthesis gas separation device, the hydrogen circulation regulating valve and the CO circulation regulating valve are closed, CO is directly obtained as a CO product after being treated by the CO compressor, and crude H is obtained2The hydrogen is separated into pure hydrogen product and desorbed gas by a pressure swing adsorption unit, and the desorbed gas returns to the raw material pipeline for circulation by a desorbed gas compressor.
Furthermore, when it is desired to replace the feedstock from crude carbon monoxide to synthesis gas, it is conventional to shut down the plant, replace it with nitrogen, and then reintroduce the synthesis gas. This is time and labor consuming and costly. The invention is used in a synthesis gas separation deviceThe added 1) CO product returns to a CO circulating pipeline and a regulating valve of the raw material pipeline; 2) h2The product returns to the hydrogen circulation pipeline and the regulating valve of the raw material pipeline; 3) a tail gas circulation pipeline is led out of the tail gas discharge pipeline and is connected with the raw material pipeline; by adjusting the amount of returned CO and the amount of H2 of the system, the device can keep stable operation in the process of converting the feed from the crude carbon monoxide into the synthesis gas, and the product CO can keep a qualified and stable supply state, thereby saving the time and cost for stopping and starting compared with the traditional method. Compared with the prior art, the method of the invention saves the time and cost for stopping and driving compared with the traditional method.
Drawings
FIG. 1 is a flow diagram of a system for switching raw CO to syngas without stopping the syngas separation plant of the present invention.
The reference numbers in the figures indicate:
1. the system comprises a temperature swing adsorption unit, a 2 cold box, a 3 CO compressor, a 4 pressure swing adsorption unit, a 5 desorbed gas compressor, a 6 hydrogen supplement pipeline, a 7 CO product pipeline, a 8 CO circulation pipeline, a 9 hydrogen product pipeline, a 10 hydrogen circulation pipeline, a 11 hydrogen regulating valve, a 12 CO product regulating valve, a 13 CO circulation regulating valve, a 14 tail gas discharge pipeline, a 15 tail gas regulating valve, a 16 hydrogen circulation regulating valve, a 17 raw material pipeline, a 18 tail gas circulation pipeline, a 19 tail gas circulation regulating valve, a 20 circulating gas compressor.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Examples
A system for switching raw material crude CO into synthetic gas by a synthetic gas separation device without stopping a vehicle is shown in figure 1 and comprises the synthetic gas separation device, wherein the synthetic gas separation device comprises a temperature swing adsorption unit 1, a cold box 2, a CO compressor 3, a pressure swing adsorption unit 4 and a desorption gas compressor 5, an inlet of the temperature swing adsorption unit 1 is connected with a raw material pipeline 17, the raw material pipeline 17 is used for accessing crude carbon monoxide or synthetic gas, an outlet of the temperature swing adsorption unit 1 is connected with an inlet of the cold box 2, one outlet of the cold box 2 is connected with an inlet of the CO compressor 3, the CO compressor 3 is provided with two outlets, one outlet is connected with a CO product pipeline 7, the other outlet is connected back to the cold box 2, circulation is formed between the cold box 2 and the CO compressor 3, and the other outlet of the cold box 2 is sequentially connected with the pressure swing adsorption unit 4 and the desorption gas compressor 5, the outlet of the desorption gas compressor 5 is connected with the inlet of the temperature swing adsorption unit 1 to form circulation, the pressure swing adsorption unit 4 is also provided with another outlet connected with a hydrogen product pipeline 9, the CO product pipeline 7 leads out a CO circulation pipeline 8, the CO circulation pipeline 8 is connected with a raw material pipeline 17, the hydrogen product pipeline 9 leads out a hydrogen circulation pipeline 10, the hydrogen circulation pipeline 10 is connected with the raw material pipeline 17, the outlet of the cold box 2 is also provided with a tail gas discharge pipeline 14, the tail gas discharge pipeline 14 leads out a tail gas circulation pipeline 18, and the tail gas circulation pipeline 18 is connected with the raw material pipeline 17; the raw material pipeline 17 is also connected with a hydrogen replenishing pipeline 6.
Wherein, a hydrogen regulating valve 11 for regulating the hydrogen flow is arranged on the hydrogen supplementing pipeline 6. And a CO product regulating valve 12 is arranged on the CO product pipeline 7, and the CO circulating pipeline 8 is arranged in front of the CO product regulating valve 12 according to the flow direction of gas in the CO product pipeline 7. A CO circulation regulating valve 13 is arranged on the CO circulation pipeline 8. The hydrogen circulation pipeline 10 is provided with a hydrogen circulation regulating valve 16 for regulating the flow rate of the circulating hydrogen. And a tail gas regulating valve 15 is arranged on the tail gas discharge pipeline 14. The exhaust gas circulation line 18 is arranged in front of the exhaust gas regulating valve 15 according to the flow direction of the exhaust gas in the exhaust gas discharge line 14. And a tail gas circulation regulating valve 19 and a circulating gas compressor 20 are arranged on the tail gas circulation pipeline 18.
The temperature swing adsorption unit, the pressure swing adsorption unit and the cold box are all conventional device structures for purifying industrial gas, and a person skilled in the art can select from the conventional temperature swing adsorption unit, the pressure swing adsorption unit and the cold box.
Referring to fig. 1, a method for switching raw CO to syngas without shutting down a syngas separation plant is based on a system for switching raw CO to syngas without shutting down a syngas separation plant, the method comprising the steps of: by adjusting the amount of the CO product in the CO circulating pipeline 8 returned to the raw material pipeline 17 and the amount of the hydrogen in the hydrogen circulating pipeline 10 returned to the raw material pipeline 17, the system can keep stable operation in the process of converting the gas in the raw material pipeline 17 from the crude carbon monoxide into the synthesis gas, and the product CO supplied by the CO product pipeline 7 can keep a qualified and stable supply state.
Wherein, the content of the components in the crude carbon monoxide is as follows: h20-1％，CH40-1％，N2+ Ar 0-0.5%, and the balance CO.
Wherein the content of the components in the synthesis gas is as follows: CO content 40-60%, N2+Ar 0-0.2％，CH40-1% of the total weight of the composition, and the balance of the composition is H2。
In the conversion of the gas from crude carbon monoxide to synthesis gas in the feed line 17, the following process is used:
A. maintaining the syngas separation plant load at 50% of the design feed rate, slowly injecting the raw syngas into the raw pipeline 17 while slowly reducing the injection of crude carbon monoxide;
B. stopping the hydrogen injection after the hydrogen content in the feed line 17 exceeds 2%;
C. starting the synthesis gas separation device, keeping a full circulation state, compressing the circulating tail gas in the tail gas circulating pipeline 18 by a circulating gas compressor 20, and returning the compressed circulating tail gas to the raw material pipeline 17;
D. the flow of the raw material synthesis gas is continuously increased and the flow of the crude carbon monoxide is reduced, the amount of the CO product in the CO circulating pipeline 8 returned to the raw material pipeline 17, the amount of the hydrogen in the hydrogen circulating pipeline 10 returned to the raw material pipeline 17 and the amount of the circulating tail gas in the tail gas circulating pipeline 18 returned to the raw material pipeline 17 are gradually adjusted;
E. when the feeding amount of the synthesis gas reaches 50% of the designed maximum feeding amount, the amount of the CO product in the CO circulating pipeline 8 returning to the raw material pipeline 17, the amount of the hydrogen in the hydrogen circulating pipeline 10 returning to the raw material pipeline 17 and the amount of the circulating tail gas in the tail gas circulating pipeline 18 returning to the raw material pipeline 17 reach the design values, at the moment, the raw material synthesis gas completely replaces the crude carbon monoxide, and the device is operated in a synthesis gas separation mode.
Wherein in step A, the rate of increase of the flow of syngas is no more than 0.5% per minute of the designed maximum feed rate and the rate of decrease of the flow of crude carbon monoxide is no more than 0.25% per minute of the designed maximum feed rate. The flow rates of the syngas increase and crude carbon monoxide decrease were maintained at about 2:1 to ensure that the flow rate of the CO component in the feed remained essentially constant.
In step B, the hydrogen content in the feed line 17 is calculated based on the composition of the crude carbon monoxide and the composition of the synthesis gas, and based on the amount of the CO product in the CO recycle line 8 returned to the feed line 17, the amount of the hydrogen in the hydrogen recycle line 10 returned to the feed line 17, and the amount of the hydrogen in the hydrogen make-up line 6. In step B, after the hydrogen content in the raw material line 17 exceeds 2%, the hydrogen circulation line 10 and the hydrogen replenishment line 6 are stopped from injecting hydrogen into the raw material line 17.
When the system for switching raw material crude CO into synthesis gas is used by the synthesis gas separation device without stopping, and crude carbon monoxide is introduced into the raw material pipeline 17, the operation method for purifying the crude carbon monoxide comprises the following steps:
a. the crude carbon monoxide raw material enters a temperature swing adsorption unit 1 to remove carbon dioxide and water, and then enters a cold box 2 to be dried and separated to form three materials, namely CO and crude H2And contain CH4The tail gas of (2);
b. coarse H2The hydrogen enters the pressure swing adsorption unit 4 for treatment, the hydrogen treated by the pressure swing adsorption unit 4 is led out from a hydrogen product pipeline 9, the desorbed gas from the pressure adsorption unit 4 also enters a desorbed gas compressor 5, and the gas discharged from the desorbed gas compressor 5 enters the temperature swing adsorption unit 1 again to form circulation;
c. CO enters a CO compressor 3, and the discharged CO is taken as a product to be delivered;
d. containing CH4The tail gas is directly discharged.
The system of this example utilizes the existing rich compression capacity of the CO compressor and the de-gasser compressor in the syngas plant to blend the CO product with H2The product is recycled to the raw material, thereby realizing the further purification of RCO into PCO by utilizing a synthesis gas separation device. When the device is used as synthesis gasWhen the separation device is used, the hydrogen circulation regulating valve and the CO circulation regulating valve are closed, CO is directly obtained after being treated by the CO compressor, and crude H is obtained2The hydrogen is separated into pure hydrogen product and desorbed gas by a pressure swing adsorption unit, and the desorbed gas returns to the raw material pipeline for circulation by a desorbed gas compressor.
Furthermore, when it is desired to replace the feedstock from crude carbon monoxide to synthesis gas, it is conventional to shut down the plant, replace it with nitrogen, and then reintroduce the synthesis gas. This is time and labor consuming and costly. The invention utilizes a CO circulating pipeline and a regulating valve which are additionally arranged on the synthesis gas separation device and return 1) CO products to the raw material pipeline; 2) h2The product returns to the hydrogen circulation pipeline and the regulating valve of the raw material pipeline; 3) a tail gas circulation pipeline is led out of the tail gas discharge pipeline and is connected with the raw material pipeline; by adjusting the amount of returned CO and the amount of H2 of the system, the device can keep stable operation in the process of converting the feed from the crude carbon monoxide into the synthesis gas, and the product CO can keep a qualified and stable supply state, thereby saving the time and cost for stopping and starting compared with the traditional method. Compared with the prior art, the system saves the time and cost for stopping and driving compared with the traditional method.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for switching raw material crude CO into synthesis gas without stopping a synthesis gas separation device is characterized in that the method is carried out based on a system for switching the raw material crude CO into the synthesis gas without stopping the synthesis gas separation device,
the system for switching raw material crude CO into synthetic gas by the synthetic gas separation device without stopping comprises the synthetic gas separation device, the synthetic gas separation device comprises a temperature swing adsorption unit (1), a cold box (2), a CO compressor (3), a pressure swing adsorption unit (4) and a desorption gas compressor (5), an inlet of the temperature swing adsorption unit (1) is connected with a raw material pipeline (17), the raw material pipeline (17) is used for accessing crude carbon monoxide or synthetic gas, an outlet of the temperature swing adsorption unit (1) is connected with an inlet of the cold box (2), one outlet of the cold box (2) is connected with an inlet of the CO compressor (3), the CO compressor (3) is provided with two outlets, one outlet is connected with a CO product pipeline (7), and the other outlet is connected back to the cold box (2), so that circulation is formed between the cold box (2) and the CO compressor (3),
the other outlet of the cold box (2) is sequentially connected with a pressure swing adsorption unit (4) and a desorption gas compressor (5),
the outlet of the desorption gas compressor (5) is connected with the inlet of the temperature swing adsorption unit (1) to form circulation, the pressure swing adsorption unit (4) is also provided with another outlet connected with a hydrogen product pipeline (9),
a CO circulating pipeline (8) is led out of the CO product pipeline (7), the CO circulating pipeline (8) is connected with a raw material pipeline (17),
a hydrogen product pipeline (9) leads out a hydrogen circulating pipeline (10), the hydrogen circulating pipeline (10) is connected with a raw material pipeline (17),
the outlet of the cold box (2) is also provided with a tail gas discharge pipeline (14), a tail gas circulation pipeline (18) is led out of the tail gas discharge pipeline (14), and the tail gas circulation pipeline (18) is connected with a raw material pipeline (17);
the raw material pipeline (17) is also connected with a hydrogen supplementing pipeline (6);
the method comprises the following steps:
by adjusting the amount of the CO product in the CO circulating pipeline (8) returning to the raw material pipeline (17) and the amount of the hydrogen in the hydrogen circulating pipeline (10) returning to the raw material pipeline (17), the system can keep stable operation in the process of converting the gas in the raw material pipeline (17) from the crude carbon monoxide into the synthetic gas, and the product CO supplied by the CO product pipeline (7) can keep a qualified and stable supply state.
2. The process for switching raw CO to syngas without stopping the syngas separation plant of claim 1,
the crude carbon monoxide comprises the following components in percentage by weight: h20-1％，CH40-1％，N2+ Ar 0-0.5%, and the balance CO;
the synthesis gas comprises the following components in content: CO content 40-60%, N2+Ar 0-0.2％，CH40-1% of the total weight of the composition, and the balance of the composition is H2。
3. A process for switching raw CO to synthesis gas without stopping the synthesis gas separation unit according to claim 1, wherein the following process is used in the conversion of the gas from raw carbon monoxide to synthesis gas in the raw line (17):
A. maintaining the syngas separation plant load at 50% of the design feed rate, slowly injecting raw syngas into the raw pipeline (17) while slowly reducing the injection of crude carbon monoxide;
B. stopping hydrogen injection after the hydrogen content in the feed line (17) exceeds 2%;
C. starting a synthesis gas separation device, keeping a full-circulation state, compressing the circulating tail gas in a tail gas circulating pipeline (18) by a circulating gas compressor (20), and returning the compressed circulating tail gas to a raw material pipeline (17);
D. continuously increasing the flow of the raw material synthesis gas and reducing the flow of the crude carbon monoxide, and gradually adjusting the amount of the CO product in the CO circulation pipeline (8) returning to the raw material pipeline (17), the amount of the hydrogen in the hydrogen circulation pipeline (10) returning to the raw material pipeline (17), and the amount of the circulation tail gas in the tail gas circulation pipeline (18) returning to the raw material pipeline (17);
E. when the feeding amount of the synthesis gas reaches 50% of the designed maximum feeding amount, the amount of the CO product in the CO circulating pipeline (8) returning to the raw material pipeline (17), the amount of the hydrogen in the hydrogen circulating pipeline (10) returning to the raw material pipeline (17), and the amount of the circulating tail gas in the tail gas circulating pipeline (18) returning to the raw material pipeline (17) reach the designed values, at the moment, the raw material synthesis gas completely replaces crude carbon monoxide, and the device is operated in a synthesis gas separation mode.
4. The process for switching raw crude CO to syngas without stopping the syngas separation plant of claim 3 wherein in step A, the syngas flow rate is increased by no more than 0.5% per minute at the designed maximum feed rate and the crude CO flow rate is decreased by no more than 0.25% per minute at the designed maximum feed rate.
5. A process for switching raw CO to synthesis gas without stopping the synthesis gas separation plant according to claim 3, wherein in step B the hydrogen content in the raw line (17) is calculated from the composition of the raw carbon monoxide, the composition of the synthesis gas and from the amount of CO product in the CO recycle line (8) returned to the raw line (17) and the amount of hydrogen in the hydrogen recycle line (10) returned to the raw line (17) and the amount of hydrogen in the hydrogen make-up line (6).
6. A process for switching raw CO to synthesis gas without stopping the synthesis gas separation plant according to claim 5, wherein in step B, the hydrogen recycle line (10) and the hydrogen make-up line (6) are stopped from injecting hydrogen into the raw line (17) after the hydrogen content in the raw line (17) exceeds 2%.
7. The method for switching raw material crude CO into synthesis gas without stopping the synthesis gas separation device according to claim 1, wherein when the system for switching raw material crude CO into synthesis gas without stopping the synthesis gas separation device is used, and crude carbon monoxide is introduced into the raw material pipeline (17), the operation method for purifying the crude carbon monoxide comprises the following steps:
1) the crude carbon monoxide raw material enters a temperature swing adsorption unit (1) to remove carbon dioxide and water, and then enters a cold box (2) to be dried and separated to form three strands of materials, namely CO and crude H2And contain CH4The tail gas of (2);
2) coarse H2The hydrogen enters a pressure swing adsorption unit (4) for treatment, the hydrogen treated by the pressure swing adsorption unit (4) is led out from a hydrogen product pipeline (9), desorbed gas from the pressure swing adsorption unit (4) also enters a desorbed gas compressor (5), and gas discharged from the desorbed gas compressor (5) enters the temperature swing adsorption unit (1) again to formCirculating;
3) CO enters a CO compressor (3), and the discharged CO is taken as a product to be delivered;
4) containing CH4The tail gas is directly discharged.
8. A method for switching raw CO to synthesis gas without stopping the synthesis gas separation plant according to claim 1, characterized in that a hydrogen regulating valve (11) for regulating the hydrogen flow rate is further arranged on the hydrogen supply line (6);
and a CO product regulating valve (12) is arranged on the CO product pipeline (7), and the CO circulating pipeline (8) is arranged in front of the CO product regulating valve (12) according to the gas flow direction in the CO product pipeline (7).
9. A method for switching raw CO to synthesis gas without stopping the synthesis gas separation plant according to claim 1, characterized in that a CO circulation regulating valve (13) is arranged on the CO circulation line (8); a hydrogen circulation regulating valve (16) for regulating the flow of circulating hydrogen is arranged on the hydrogen circulation pipeline (10);
a tail gas regulating valve (15) is arranged on the tail gas discharge pipeline (14), the tail gas flow direction in the tail gas discharge pipeline (14) is determined, and a tail gas circulating pipeline (18) is arranged in front of the tail gas regulating valve (15).
10. The method for switching raw CO to synthesis gas without stopping the synthesis gas separation plant according to claim 1, characterized in that a tail gas circulation regulating valve (19) is arranged on the tail gas circulation pipeline (18).
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