CN219942763U - System for preparing methanol by carbon dioxide hydrogenation - Google Patents
System for preparing methanol by carbon dioxide hydrogenation Download PDFInfo
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- CN219942763U CN219942763U CN202321159993.8U CN202321159993U CN219942763U CN 219942763 U CN219942763 U CN 219942763U CN 202321159993 U CN202321159993 U CN 202321159993U CN 219942763 U CN219942763 U CN 219942763U
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- Prior art keywords
- gas
- methanol
- carbon dioxide
- separator
- inlet pipe
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 240
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 62
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 62
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 61
- 239000012528 membrane Substances 0.000 claims abstract description 46
- 238000001816 cooling Methods 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract 2
- 238000001514 detection method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000498 cooling water Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model discloses a methanol preparation system by carbon dioxide hydrogenation, which comprises a methanol reactor, a membrane separator, a cooling heat exchanger I, a gas-liquid separator and a feeding pipe, wherein the feeding pipe is used for inputting mixed gas of carbon dioxide and hydrogen into a feed inlet of the methanol reactor, a product outlet of the methanol reactor is connected to an inlet of the membrane separator through a pipeline, the membrane separator is used for separating methanol from the mixed product, a first outlet of the membrane separator outputs the separated methanol outwards, a second outlet of the separator is connected to the gas-liquid separator through the cooling heat exchanger I, the cooling heat exchanger I is used for cooling water in the mixture into a liquid state, a liquid outlet of the gas-liquid separator outwards discharges water, and a gas outlet of the gas-liquid separator is connected to the feeding pipe through a raw material recovery pipe. The utility model does not need to heat the output substances, thereby greatly reducing the energy consumption and ensuring the separation effect of the methanol.
Description
Technical Field
The utility model belongs to the technical field of carbon dioxide resource utilization, and particularly relates to a system for preparing methanol by carbon dioxide hydrogenation.
Background
One of the recycling methods of the carbon dioxide is to hydrogenate the carbon dioxide, react under the action of a catalyst to prepare the methanol, realize emission reduction of the carbon dioxide, recycle the carbon dioxide, convert the carbon dioxide into the methanol, and can be used as a chemical raw material and a chemical energy source. In the existing technology for preparing methanol by hydrogenating carbon dioxide, carbon dioxide and hydrogen are conveyed into a methanol reactor to synthesize methanol and water under high-temperature and high-pressure conditions, but raw materials, especially hydrogen, have little residue after reaction due to small single-pass conversion rate, so that gas components at the outlet of the reactor consist of hydrogen, carbon dioxide, methanol (in a gaseous state), water (in a gaseous state) and the like. In order to obtain a reaction product with higher purity and recycle the residual raw materials, the mixed gas is cooled by a heat exchanger, and the product (methanol and water) and raw material gas (hydrogen and carbon dioxide) are separated by gas-liquid separation. The separated raw material gas is recycled, and the crude methanol product containing water enters a rectification system for purification.
The above-described technique has the following problems.
1. The per pass conversion of carbon dioxide is typically less than 30% and therefore separation of the product from the unreacted complete feed gas is required. A method of cooling the gas-liquid separator is generally adopted. This process cools the product, but subsequent rectification and heating is required, so multiple heat exchangers are required. Repeated increases and decreases in temperature also result in more energy loss.
2. Compared with the industrialized production of methanol by hydrogenation of carbon monoxide, the production of methanol by hydrogenation of carbon dioxide can produce a large amount of water, so that the energy consumption of the subsequent rectification and purification is greatly increased.
Disclosure of Invention
The utility model provides a system for preparing methanol by hydrogenating carbon dioxide, which is used for solving the technical problems that in the prior art, a mixed product obtained by a reactor needs repeated temperature rise and fall in the process of separating, purifying and recycling residual raw materials, so that more energy consumption is caused, the water content in a reaction product is more, and the energy consumption for heating and purifying is larger.
The system for preparing the methanol by hydrogenating the carbon dioxide comprises a methanol reactor, a membrane separator, a cooling heat exchanger I, a gas-liquid separator and a feeding pipe, wherein the feeding pipe is used for inputting mixed gas of the carbon dioxide and the hydrogen into a feed inlet of the methanol reactor, a product outlet of the methanol reactor is connected to an inlet of the membrane separator through a pipeline, the membrane separator is used for separating the methanol from the mixed product, a first outlet of the membrane separator is used for outputting the separated methanol outwards, a second outlet of the separator is connected to the gas-liquid separator through the cooling heat exchanger I, the cooling heat exchanger I is used for cooling water in the mixture into a liquid state, a liquid outlet of the gas-liquid separator is used for discharging water outwards, and a gas outlet of the gas-liquid separator is connected to the feeding pipe through a raw material recovery pipe.
Preferably, a gas separation membrane is arranged in the membrane separator, and the gas separation membrane separates the mixed products of the gases according to different kinetic diameters of substances.
Preferably, the system for preparing methanol by hydrogenation of carbon dioxide further comprises a first air inlet pipe connected with a carbon dioxide air source and a second air inlet pipe connected with a hydrogen air source, and the first air inlet pipe and the second air inlet pipe are connected to the feeding pipe in parallel through corresponding compressors respectively.
Preferably, a detection branch is arranged between the branch of the feeding pipe and the outlet of the feeding pipe, the detection branch is connected to a gas detection instrument, and the gas detection instrument is used for detecting the ratio of carbon dioxide to hydrogen in the raw material gas.
Preferably, the first outlet may be further connected to a drying device and a cooling device in sequence, the cooling device being used for liquefying the separated methanol gas.
Preferably, a product outlet of the methanol reactor is connected to the membrane separator through a second cooling heat exchanger.
The utility model has the following advantages: the utility model can adjust the ratio of carbon dioxide to hydrogen in the feed gas, thereby ensuring higher conversion rate of carbon dioxide in the reaction. The materials output by the methanol reactor are not required to be heated again in the steps of gas membrane separation, heat exchange cooling, gas-liquid separation and the like, so that the energy consumption is greatly reduced, the separation effect of the methanol can be ensured by the membrane reactor, and the recovery of residual raw materials after separation is realized by the connection structure of the separation structure and the raw material recovery pipe.
Drawings
FIG. 1 is a schematic diagram of a system for producing methanol by hydrogenating carbon dioxide according to the present utility model.
The marks in the drawings are: 1. the device comprises a compressor, a feeding pipe, a methanol reactor, a membrane separator, a raw material recovery pipe, a cooling heat exchanger I, a gas-liquid separator I, a gas detection instrument II, a first air inlet pipe, a second air inlet pipe, a cooling heat exchanger II, a gas detection instrument II, a first air inlet pipe, a second air inlet pipe, a first air inlet pipe and a cooling heat exchanger II.
Detailed Description
The following detailed description of the embodiments of the utility model, given by way of example only, is presented in the accompanying drawings to aid in a more complete, accurate, and thorough understanding of the inventive concepts and aspects of the utility model by those skilled in the art.
As shown in fig. 1, the utility model provides a methanol-to-carbon dioxide hydrogenation system, which comprises a methanol reactor 3, a membrane separator 4, a first cooling heat exchanger 11, a gas-liquid separator 7 and a feed pipe 2, wherein the feed pipe 2 is used for inputting mixed gas of carbon dioxide and hydrogen into a feed port of the methanol reactor 3, the methanol reactor 3 is used for realizing the reaction of preparing methanol and water from carbon dioxide hydrogenation gas, a product outlet of the methanol reactor 3 is connected to an inlet of the membrane separator 4 through a pipeline, the membrane separator 4 is used for separating methanol from mixed products, a first outlet of the membrane separator 4 outputs separated methanol outwards, a second outlet of the separator is connected to the gas-liquid separator 7 through the first cooling heat exchanger 11, the first cooling heat exchanger 11 is used for cooling a mixture separated by the membrane separator 4, water in the mixture is cooled into a liquid state by the first cooling heat exchanger 11, the cooled mixture is subjected to gas-liquid separation by the gas-liquid separator 7, a liquid outlet of the gas-liquid separator 7 discharges the separated methanol outwards, and the gas-liquid is connected to the feed pipe 5 through the gas-liquid separator 7.
The membrane separator 4 is provided with a gas separation membrane, and the gas separation membrane separates the mixed products of the gases according to different kinetic diameters of substances. The separation method does not need repeated heating and cooling of the product, has reliable separation effect, and can effectively avoid leakage of methanol or recovery or leakage of methanol mixed in safe substances. Therefore, the method can avoid the harm of methanol, which is toxic, to the surrounding environment and operators, and has the advantages of high separation efficiency and no need of heating. Specifically, the gas separation membrane adopts an organic polymer membrane, and the main component of the gas separation membrane is one of polyimide, polysulfone, cellulose, polyaniline, silicon-containing polymer and other organic polymer substances.
The product outlet of the methanol reactor 3 is connected to the membrane separator 4 through a second cooling heat exchanger 6. Because the gas separation membrane in the membrane separator 4 has poor heat resistance, the temperature of the gas product obtained through the reaction is too high, and the gas product is required to be cooled to a lower temperature through the second cooling heat exchanger 6 so as to be suitable for being input into the membrane separator 4 for separation. Meanwhile, the pressure difference at two sides of the gas separation membrane is controlled to be not more than 1MPa, so that the normal use of the membrane separator 4 is ensured.
The system for preparing methanol by hydrogenating carbon dioxide further comprises a first air inlet pipe 9 connected with a carbon dioxide air source and a second air inlet pipe 10 connected with a hydrogen air source, wherein the first air inlet pipe 9 and the second air inlet pipe 10 are respectively connected with the feeding pipe 2 in parallel through corresponding compressors 1, and the feeding pipe 2 comprises a recycling branch connected with the raw material recycling pipe 5. Through this structure, this system mixes the carbon dioxide and the hydrogen after the pressurization and sends into methanol reactor 3 to satisfy the required pressure of methanol reactor 3 to realize the recovery to the residual raw materials in the product.
A detection branch is arranged between the branch of the feeding pipe 2 and the outlet of the feeding pipe 2, the detection branch is connected to a gas detection instrument 8, and the gas detection instrument 8 is used for detecting the ratio of carbon dioxide to hydrogen in the raw material gas. Under the conditions of high temperature and high pressure in the methanol reactor 3, methanol and water are generated through the hydrogenation reaction of carbon dioxide under the catalysis of a catalyst, and the reaction formula is as follows: CO 2 + 3H 2 →CH 3 OH+ H 2 O. The conventional molar ratio of carbon dioxide to hydrogen is 1:3, but the conversion of carbon dioxide obtained by this input into the methanol reactor 3 is only 37%, wherein the selectivity for methanol is 72% (i.e. 37% of carbon dioxide reacts and 72% of the reacted portion becomes methanol). When the hydrogen partial pressure was further increased to a carbon dioxide to hydrogen molar ratio of 1:10, a sharp increase in both carbon dioxide conversion and methanol selectivity was observed, at which ratio the carbon dioxide conversion was very high, reaching 95%.
Therefore, in order to ensure that the molar ratio of carbon dioxide to hydrogen is not lower than 1:10, and the gas after separation of the products can be recovered before and after recovery, the method detects the ratio of carbon dioxide to hydrogen by arranging a detection instrument at the corresponding position of the feed pipe 2, adjusts the ratio of the carbon dioxide to the hydrogen by controlling the air supply amount of the hydrogen or a carbon dioxide air source, and adjusts the corresponding air supply amount according to the detected ratio after recovery of the separated gas (the main component is hydrogen and contains a small amount of carbon dioxide and water vapor).
The first outlet can be sequentially connected with a drying device and a cooling device, the drying device further absorbs and dries water vapor remained in the methanol gas (a drying agent such as calcium oxide can be adopted, the drying agent does not react with the methanol), and the cooling device is used for liquefying the separated methanol gas so as to be convenient for discharging and collecting.
The carbon dioxide gas source is high-heat waste gas, and the high-heat waste gas is purified by a dust removing device, a denitration device and a desulfurization device and then is input into the first air inlet pipe 9. The carbon dioxide thus fed is a high-temperature gas, so that a hydrogen gas source and a recovered raw material gas can be added, reducing the energy consumption required for heating the raw material in the methanol reactor 3.
The working process of the system is as follows: the high-heat waste gas is purified by a dust removing device, a denitration device and a desulfurization device and then is input into a first air inlet pipe 9 as a carbon dioxide air source, and then is pressurized by a compressor 1 and then enters a first air inlet branch of the air inlet pipe, and a stored hydrogen air source is pressurized by a second air inlet pipe 10 and the compressor 1 and then enters a second air inlet branch of the air inlet pipe. The raw material gas mixed in the gas inlet pipe is input into the methanol reactor 3.
The temperature of the raw material gas is higher because the input carbon dioxide gas source comes from the high-temperature waste gas, the internal pressure is pressurized by the compressor 1, the internal pressure has higher pressure, the raw material gas is converted into methanol and water under the action of the reaction structure of the catalyst attached in the methanol reactor 3, and the system adjusts the ratio of carbon dioxide to hydrogen by detecting the ratio of each gas in the raw material gas before, so that higher carbon dioxide conversion rate can be obtained.
The product obtained by the reaction is then conveyed to a membrane separator 4 through a pipeline, and the separation of methanol gas and other gases is realized through a gas membrane separation method. The mixed output of the product including the protected product includes methanol, water, residual hydrogen and carbon dioxide (trace amounts) from the reaction, and other impurities. Among the major species that occupy a relatively high proportion, the kinetic diameters of hydrogen and water are extremely small, the diffusion rate is high, and permeation through the membrane is easy. Whereas methanol has a large kinetic diameter and is difficult to permeate through the membrane. Therefore, the gas separation membrane is used for separating hydrogen and water, and has high selectivity. The separated hydrogen and water are separated by the gas-liquid separator 7 after being cooled by the first cooling heat exchanger 11.
Obviously, in the working process, the substances output by the methanol reactor 3 do not need to be heated again in the steps of gas membrane separation, heat exchange cooling, gas-liquid separation and the like, so that the energy consumption is greatly reduced, and the heat-conducting medium obtained by heat exchange cooling of the substances can further recover and utilize the heat.
While the utility model has been described above with reference to the accompanying drawings, it will be apparent that the utility model is not limited to the above embodiments, but is capable of being modified or applied to other applications without modification, as long as various insubstantial modifications of the inventive concept and technical solutions are adopted, all within the scope of the utility model.
Claims (6)
1. A methanol preparation system by carbon dioxide hydrogenation is characterized in that: including methanol reactor (3), membrane separator (4), cooling heat exchanger one (11), gas-liquid separator (7) and inlet pipe (2), inlet pipe (2) are used for to the feed inlet of methanol reactor (3) inputts the mixed gas of carbon dioxide and hydrogen, the product export of methanol reactor (3) is connected to through the pipeline membrane separator (4) entry, membrane separator (4) are used for separating out the methanol from mixed product, the first export of membrane separator (4) outwards exports the methanol that the separation obtained, the second export of separator is passed through cooling heat exchanger one (11) is connected to gas-liquid separator (7), cooling heat exchanger one (11) are arranged in being in the water cooling in the mixture that membrane separator (4) separated is liquid, the liquid export of gas-liquid separator (7) outwards discharges water, the gas export of gas-liquid separator (7) is connected to through raw materials recovery pipe (5) inlet pipe (2).
2. The system for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the membrane separator (4) is internally provided with a gas separation membrane which is used for separating the mixed products of the gases according to different kinetic diameters of substances.
3. The system for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the system for preparing methanol by hydrogenating carbon dioxide further comprises a first air inlet pipe (9) connected with a carbon dioxide air source and a second air inlet pipe (10) connected with a hydrogen air source, wherein the first air inlet pipe (9) and the second air inlet pipe (10) are connected in parallel to the feeding pipe (2) through corresponding compressors (1) respectively.
4. The system for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: a detection branch is arranged between a branch of the feeding pipe (2) and an outlet of the feeding pipe (2), the detection branch is connected to a gas detection instrument (8), and the gas detection instrument (8) is used for detecting the ratio of carbon dioxide to hydrogen in raw material gas.
5. The system for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the first outlet may also be connected in sequence to a drying device and a cooling device for liquefying the separated methanol gas.
6. The system for preparing methanol by hydrogenating carbon dioxide according to claim 1, wherein: the product outlet of the methanol reactor (3) is connected to the membrane separator (4) through a second cooling heat exchanger (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202321159993.8U CN219942763U (en) | 2023-05-12 | 2023-05-12 | System for preparing methanol by carbon dioxide hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202321159993.8U CN219942763U (en) | 2023-05-12 | 2023-05-12 | System for preparing methanol by carbon dioxide hydrogenation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN219942763U true CN219942763U (en) | 2023-11-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202321159993.8U Active CN219942763U (en) | 2023-05-12 | 2023-05-12 | System for preparing methanol by carbon dioxide hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN219942763U (en) |
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2023
- 2023-05-12 CN CN202321159993.8U patent/CN219942763U/en active Active
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