CN111747411A - Low-pressure low-temperature treatment method for industrial carbon dioxide gas - Google Patents
Low-pressure low-temperature treatment method for industrial carbon dioxide gas Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
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Abstract
The invention discloses a low-pressure low-temperature treatment method of industrial carbon dioxide gas, which comprises the steps of (1) enabling carbon dioxide raw gas to enter a field washing tower from upstream through a pipeline, enabling the gas to enter a compression process after washing, cooling and dehydrating, and enabling the temperature of the carbon dioxide gas to be reduced to be lower than 2 ℃; (2) the low-temperature carbon dioxide compressed gas is conveyed to a washing tower to be washed, low-temperature purified water and the carbon dioxide compressed gas are adopted for heat exchange, and (3) the washed carbon dioxide gas is subjected to a heat exchange cooling process to obtain low-pressure low-temperature pure carbon dioxide gas. The scheme of the invention can efficiently and effectively dehydrate and remove impurities, has scientific treatment method, greatly reduces the loss of carbon dioxide, and is environment-friendly and energy-saving.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide purification and dehydration.
Background
The carbon dioxide feed gas contains various impurities such as water, light hydrocarbons, methanol, sulfur, and the like. The water content is much higher than the other impurities. When the liquid carbon dioxide can be used as a drying agent and used for manufacturing dry ice and the like, the water content in the product cannot exceed the standard, and the technological process needs to be strictly controlled. The existing carbon dioxide dehydration process device mainly comprises a pressure swing adsorption dehydration device and liquefaction purification low-temperature rectification.
The pressure swing adsorption dehydration device generates solid waste in the dehydration process, is not beneficial to the production idea of green environmental protection at present, needs a clean storage tank gas source to sweep and regenerate the adsorbent, and is quite uneconomical and poor in product quality stability.
Liquefaction, purification and low-temperature rectification: the process is established on the basis of low water content of an air source, and achieves the aim of removing water in a rectification mode, the process environment temperature is generally about minus 20 ℃, the required cold quantity is large, and the energy consumption is also large; the temperature control is harsh, if the temperature control is too high, the aim of water removal cannot be achieved, and the temperature control is too low, so that the imagination that the pipeline and the tank body are blocked by ice can be generated, and the production is influenced.
The existing treatment method for industrial carbon dioxide gas cannot efficiently dehydrate and remove impurities, has complex process and high difficulty in controlling the process, consumes large energy and is not environment-friendly.
Disclosure of Invention
The invention aims to provide a low-pressure low-temperature treatment method for industrial carbon dioxide gas, which solves the problems in the background art, can efficiently dehydrate and remove impurities, is scientific in treatment method, greatly reduces the loss of carbon dioxide, and is environment-friendly and energy-saving.
The invention provides a low-pressure low-temperature treatment method of industrial carbon dioxide gas, which comprises the following steps
(1) Feeding carbon dioxide raw material gas into an on-site water washing tower from upstream through a pipeline, and after water washing, cooling and dehydrating, feeding the gas into a compression process, wherein the temperature of the carbon dioxide gas is reduced to below 2 ℃;
(2) conveying low-temperature carbon dioxide compressed gas to a water washing tower for water washing, adopting low-temperature purified water to exchange heat with the carbon dioxide compressed gas, and liquefying and dissolving methanol and water in the carbon dioxide compressed gas in the heat exchange process to form methanol water solution which is taken to the bottom of the tower and then discharged to the outside through the bottom of the tower; returning part of the water to the cooler through the water washing process water circulating pump for cooling, and then entering the water washing tower for circulation;
(3) and (4) carrying out heat exchange and cooling processes on the washed carbon dioxide gas to obtain low-pressure low-temperature pure carbon dioxide gas.
Further, the step (2) comprises that the carbon dioxide raw material gas contains various impurities, including moisture, light hydrocarbon impurities, methanol and sulfur particles, and the carbon dioxide raw material gas is subjected to water washing heat exchange through a water washing tower, and the freezing point is reduced through the characteristics of a methanol water solution; when methanol mixed with a corresponding proportion in water can prevent freezing, the larger the mass fraction of the methanol is, the lower the freezing point is;
the water is in a supersaturated environment, the evaporation temperature of the water is reduced, the water exists in a liquid form all the time, the liquid water is always deposited at the bottom of the tower, the water is conveniently removed, and water vapor is not generated.
Further, the step (2) also comprises controlling the reaction of the carbon dioxide and the water to reach dynamic equilibrium, generating carbonic acid after the carbon dioxide is continuously dissolved in the water, and decomposing the carbonic acid to supplement the lost carbon dioxide.
Further, in the step (1), the carbon dioxide raw material gas is controlled to be at the original temperature of more than 35 ℃ and the original pressure of more than 0.030Mpa, the temperature is reduced to be below 2 ℃, and the pressure is reduced to be below 0.028 Mpa.
Furthermore, a heat exchange and cooling process is carried out in a cooler of the cooling system, and a plate heat exchanger is adopted as a heat exchange plate of the cooler, so that the heat exchange area is increased, and the energy consumption is reduced for the heat exchange process; and in the heat exchange process, liquid ammonia is used as a refrigerant, the liquid ammonia refrigerant is from the bottom of an ammonia liquid separator of the industrial air conditioner, gas ammonia subjected to heat exchange returns to the middle of the ammonia liquid separator through a pipeline, and finally enters an inlet of a cooler from the top of the ammonia liquid separator through the pipeline for cyclic utilization.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method provided by the invention is carried out under relatively low pressure and temperature, and by utilizing a comprehensive control technology combining factors such as water washing, temperature reduction, methanol aqueous solution property, pressure and atmospheric dew point conversion, most of water in the raw material gas is removed from the source, so that the energy consumption of the subsequent process is reduced, and meanwhile, only little gas carbon dioxide is lost in the water washing process, so that not only can the water be efficiently removed, but also the loss of the raw material can be reduced, and the process is efficient and energy-saving.
(2) The invention can obviously increase the productivity, under the condition of the same raw material gas condition, the productivity of one year in the existing process flow is 8 ten thousand tons, and the productivity is improved to 11 ten thousand tons/year by adopting the method of the invention, and the expansion is 3-4%.
(3) The method has simple control process, is carried out under relatively low pressure, has higher controllable force, does not depend on advanced chemical instruments excessively, has high reliability, and can be easily controlled under special working environment. On the contrary, the existing dehydration process works in the environment of high pressure, the high pressure means high flow rate, very high control capability is needed, the requirement on instruments is relatively high, and the price for purchasing advanced instruments is high, so that the production cost is high; and the process environment temperature is minus 20 ℃.
Drawings
FIG. 1 is a control flow diagram of the present invention;
FIG. 2 is a table of properties of aqueous methanol solutions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the present invention aims to remove moisture from carbon dioxide raw material gas with high efficiency, does not produce solid waste, and follows the production concept of green environmental protection. The refrigeration capacity is reduced in the dewatering process, the gas loss is reduced, and the production pressure is reduced for the subsequent procedures.
The invention provides a low-pressure low-temperature treatment method of industrial carbon dioxide gas, which comprises the steps of (1) enabling carbon dioxide raw gas to enter an on-site water washing tower from upstream through a pipeline, enabling the gas to enter a compression process after water washing, temperature reduction and dehydration, and enabling the temperature of the carbon dioxide gas to be reduced to be below 2 ℃. Controlling the original temperature of the carbon dioxide feed gas to be more than 35 ℃, the original pressure to be more than 0.030Mpa, the original temperature to be lower than 2 ℃, and the original pressure to be lower than 0.028 Mpa. For example, the raw material gas of one embodiment is reduced from the original 40 ℃/0.031Mpa to 0.8 ℃/0.026 Mpa.
Conveying low-temperature carbon dioxide compressed gas to a washing tower for washing, exchanging heat with the carbon dioxide compressed gas by adopting low-temperature purified water, liquefying and dissolving methanol and water in the carbon dioxide compressed gas into methanol water solution in the heat exchange process, bringing the methanol water solution to the tower bottom, and discharging the methanol water solution to the outside through the tower bottom; and returning part of the water to the cooler through the water washing process water circulating pump for cooling, and then entering the water washing tower for circulation.
For example, the water washing process water is a pure water with the temperature of 0.5 ℃ and the pressure of 0.029 MPa. It enters the water washing tower from the water washing process water cooler through a pipeline and exchanges heat with the feed gas. After heat exchange, the temperature of the process water is 12 ℃ and the pressure is unchanged. The carbon dioxide feed gas contains various impurities, including water, light hydrocarbon impurities, methanol and sulfur particles, and the carbon dioxide feed gas is subjected to water washing heat exchange through a water washing tower, so that the freezing point is reduced by the characteristics of a methanol aqueous solution; when methanol mixed with corresponding proportion in water can prevent freezing, the larger the mass fraction of the methanol is, the lower the freezing point is, and the regulation can be reasonably controlled according to the rule discovered by the inventor;
the water is in a supersaturated environment, the evaporation temperature of the water is reduced, the water exists in a liquid form all the time, the liquid water is always deposited at the bottom of the tower, the water is conveniently removed, and water vapor is not generated.
Further, the step (2) also comprises controlling the reaction of the carbon dioxide and the water to reach dynamic equilibrium, generating carbonic acid after the carbon dioxide is continuously dissolved in the water, and decomposing the carbonic acid to supplement the lost carbon dioxide. Due to the special properties of gaseous carbon dioxide, carbon dioxide reacts to form carbonic acid when dissolved in water. The reaction of carbon dioxide and water is a reversible reaction, i.e. both sides of the reaction are carried out simultaneously to achieve dynamic equilibrium, when carbon dioxide is continuously dissolved in water, carbonic acid is generated, and carbonic acid is also decomposed to 'compensate' the lost carbon dioxide. There is little loss of carbon dioxide feed during this water removal process.
And (4) carrying out heat exchange and cooling on the carbon dioxide gas washed in the step (3) to obtain low-pressure low-temperature pure carbon dioxide gas.
The heat exchange and cooling process is carried out in a cooler of the cooling system, and a plate heat exchanger is adopted as a heat exchange plate of the cooler, so that the heat exchange area is increased, and the energy consumption is reduced for the heat exchange process; and in the heat exchange process, liquid ammonia is used as a refrigerant, the liquid ammonia refrigerant is from the bottom of an ammonia liquid separator of the industrial air conditioner, gas ammonia subjected to heat exchange returns to the middle of the ammonia liquid separator through a pipeline, and finally enters an inlet of a cooler from the top of the ammonia liquid separator through the pipeline for cyclic utilization.
The scientific energy-saving low-pressure low-temperature dehydration principle of the invention is as follows:
the device combines theoretical knowledge of cooling, water washing, methanol water solution property and pressure, atmospheric dew point conversion and the like, obtains the feasibility of the process flow by means of data operation and simulation model operation, and obtains a good verification effect by processing industrial carbon dioxide through factory tests.
And (3) water washing process: the water washing is to wash two different soluble substances in the gas, namely, the gas carbon dioxide and the water are respectively washed simultaneously, wherein one substance (water) can be dissolved in the water, the other substance (gas carbon dioxide) cannot be dissolved, and then the water is removed by a liquid separation method (bottom discharge).
Cooling: the purpose of the temperature reduction is to keep the water in a supersaturated environment, so that the evaporation temperature of the water is reduced, and no water vapor is generated.
Referring to the table of fig. 2, it can be seen from fig. 2 that the freezing point of the aqueous methanol solution is lower than that of water. Therefore, when methanol is mixed in water in a certain proportion to prevent freezing, the higher the mass fraction of the methanol is, the lower the freezing point is. As the content of the impurities in the raw material gas is 1000ppm, the temperature of the washing process water is about 0.5 ℃, which accords with the characteristic.
The method adopts ASPEN simulation test.
On the basis of the flow diagram, a model is established in simulation software ASPEN. Accurate component data are obtained from daily analysis of raw material gas, wherein the water content is 2% -3%, and the methanol content is about 1000 ppm. The feed gas flow rate per hour was 17.90 tons. After the model is finished, the following data are obtained after the operation of the input feed gas parameters, and it can be seen that the flow of the feed gas in each hour before entering the water scrubber is 17906kg, and the flow is reduced to 17565kg/h after passing through the water scrubber, wherein the reduced part is the moisture in the feed gas, and is 341.46 kg/h. The emissions met the theoretical calculations as follows:
| raw material gas | Theoretical discharge value of liquid phase of water washing tower | |
| Medium | Mass flow rate kg/h | Mass flow rate kg/h |
| Total of | 17906 | 345 |
| CO2 | 17391 | 0.02 |
| N2 | 86.54 | 0 |
| O2 | 29.92 | 0 |
| H2O | 355.35 | 341.46 |
| CO | 0.38 | 0 |
| CH4 | 9.13 | 0 |
| CH3OH | 20.46 | 3.13 |
| H2 | 13.27 | 0 |
| C2H6 | 7.33 |
0 |
| C6H6 | 2.54 |
0 |
As can be seen, the dehydration process only consumes 0.02kg/h of gaseous carbon dioxide, which is not met by the existing carbon dioxide dehydration technology of other people, and the existing technology only consumes 0.56kg/h of gaseous carbon dioxide. Therefore, the scheme of the invention brings the advantages of obvious low raw material gas loss. The actual production verifies that the invention can obviously increase the productivity, under the condition of the same raw material gas condition, the productivity of the existing process flow is 8 ten thousand tons per year, and the productivity is improved to 11 ten thousand tons per year by adopting the method of the invention, and the expansion is 3-4%.
Claims (5)
1. The low-pressure low-temperature treatment method of the industrial carbon dioxide gas is characterized by comprising the following steps: comprises the steps of
(1) Feeding carbon dioxide raw material gas into an on-site water washing tower from upstream through a pipeline, and after water washing, cooling and dehydrating, feeding the gas into a compression process, wherein the temperature of the carbon dioxide gas is reduced to below 2 ℃;
(2) conveying low-temperature carbon dioxide compressed gas to a water washing tower for water washing, adopting low-temperature purified water to exchange heat with the carbon dioxide compressed gas, and liquefying and dissolving methanol and water in the carbon dioxide compressed gas in the heat exchange process to form methanol water solution which is taken to the bottom of the tower and then discharged to the outside through the bottom of the tower; returning part of the water to the cooler through the water washing process water circulating pump for cooling, and then entering the water washing tower for circulation;
(3) and (4) carrying out heat exchange and cooling processes on the washed carbon dioxide gas to obtain low-pressure low-temperature pure carbon dioxide gas.
2. The method for low-pressure and low-temperature treatment of industrial carbon dioxide gas according to claim 1, comprising:
the step (2) comprises that the carbon dioxide feed gas contains a plurality of impurities, including water, light hydrocarbon impurities, methanol and sulfur particles, and the carbon dioxide feed gas is subjected to water washing heat exchange in a water washing tower, and the freezing point is reduced by the characteristics of a methanol water solution; when methanol mixed with a corresponding proportion in water can prevent freezing, the larger the mass fraction of the methanol is, the lower the freezing point is;
the water is in a supersaturated environment, the evaporation temperature of the water is reduced, the water exists in a liquid form all the time, the liquid water is always deposited at the bottom of the tower, the water is conveniently removed, and water vapor is not generated.
3. The method for low-pressure and low-temperature treatment of industrial carbon dioxide gas according to claim 1, comprising:
and the step (2) also comprises controlling the reaction of the carbon dioxide and the water to reach dynamic equilibrium, generating carbonic acid after the carbon dioxide is continuously dissolved in the water, and decomposing the carbonic acid to supplement the lost carbon dioxide.
4. The method for low-pressure and low-temperature treatment of industrial carbon dioxide gas according to claim 1, comprising:
in the step (1), the carbon dioxide feed gas is controlled to be cooled to below 2 ℃ from the original temperature of above 35 ℃ and the pressure of above 0.030Mpa, and the pressure of below 0.028 Mpa.
5. The method for low-pressure and low-temperature treatment of industrial carbon dioxide gas according to claim 1, comprising:
the heat exchange and cooling process is carried out in a cooler of the cooling system, and a plate heat exchanger is adopted as a heat exchange plate of the cooler, so that the heat exchange area is increased, and the energy consumption is reduced for the heat exchange process; and in the heat exchange process, liquid ammonia is used as a refrigerant, the liquid ammonia refrigerant is from the bottom of an ammonia liquid separator of the industrial air conditioner, gas ammonia subjected to heat exchange returns to the middle of the ammonia liquid separator through a pipeline, and finally enters an inlet of a cooler from the top of the ammonia liquid separator through the pipeline for cyclic utilization.
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Cited By (1)
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| CN113769541A (en) * | 2021-09-26 | 2021-12-10 | 乔治洛德方法研究和开发液化空气有限公司 | CO generated by washing low-temperature methanol2Preparation of high pressure CO from product gas2Method and apparatus for supporting gas |
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