CN107758665A - Device and method for purifying food-grade carbon dioxide - Google Patents
Device and method for purifying food-grade carbon dioxide Download PDFInfo
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- CN107758665A CN107758665A CN201711183229.3A CN201711183229A CN107758665A CN 107758665 A CN107758665 A CN 107758665A CN 201711183229 A CN201711183229 A CN 201711183229A CN 107758665 A CN107758665 A CN 107758665A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 114
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 claims abstract description 43
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims description 61
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 58
- 229910021529 ammonia Inorganic materials 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 28
- 238000006477 desulfuration reaction Methods 0.000 claims description 21
- 230000023556 desulfurization Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 230000003009 desulfurizing effect Effects 0.000 claims description 14
- 230000006835 compression Effects 0.000 claims description 11
- 238000007906 compression Methods 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 9
- 230000000087 stabilizing effect Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 abstract description 11
- 238000002309 gasification Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract 3
- 229960004424 carbon dioxide Drugs 0.000 description 77
- 239000007789 gas Substances 0.000 description 55
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000005431 greenhouse gas 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- -1 desulfurization Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Abstract
The invention provides a device and a method for purifying food-grade carbon dioxide, which belong to the technical field of coal gasification and are used for solving the problems of overlarge energy consumption and higher operation cost when the food-grade carbon dioxide is purified by the existing low-temperature rectification method, and the device for purifying the food-grade carbon dioxide comprises the following components: the pretreatment module is used for pretreating the feed gas to obtain a first material flow; the adsorption module is used for carrying out adsorption treatment on the first material flow to obtain a second material flow; the liquefaction module is used for carrying out liquefaction treatment on the second stream to obtain a third stream; a purification module for purifying the third stream to obtain food grade carbon dioxide. The method provided by the invention can effectively remove impurities in carbon dioxide discharged by a coal gasification device, and can obtain food-grade carbon dioxide with the purity higher than 99.999%, and the method is stable and reliable, relatively low in energy consumption and low in cost.
Description
Technical field
The present invention relates to Coal Gasification Technology field, more particularly to a kind of device and method for purifying food-grade carbon-dioxide.
Background technology
Carbon dioxide is as the principal element that a kind of greenhouse gases are considered as aggravation Global Greenhouse Effect.In global climate
Under the background persistently to warm, Extreme Weather-climate Events take place frequently.Therefore, greenhouse gas emission is reduced, slows down environment and further dislikes
Change, it is imperative.
Chemical Industry has obtained significant progress as the application field of Coal Clean efficient technique of rainwater utilization in China.By
Higher in Chemical Industry concentration class, the gas concentration lwevel of discharge is high, is easy to carry out the CO concentrated on a large scale2Trapping purification and
Recycle work.
Existing food-grade carbon-dioxide purification technique mainly has Physical Absorption method, chemical absorption method, membrane separation process, low temperature
Rectification method etc., each purification technique respectively have advantage and disadvantage.The properties of gas sources of the carbon dioxide discharged according to coal gasification, often from low temperature essence
Evaporate method.All using liquefied ammonia liquid gas carbon dioxide, energy consumption is excessive for cryogenic liquefaction part in existing cryogenic rectification technology, fortune
Row cost is higher.
The content of the invention
Energy consumption is excessive during in order to solve existing cryogenic rectification method purification food-grade carbon-dioxide, and operating cost is higher to ask
Topic, properties of gas sources of the present invention for carbon dioxide in current powdered coal pressuring gasified technology, there is provided one kind can reduce liquefied gas
The device and method of the purification food-grade carbon-dioxide of body carbon dioxide usage amount is CO_2 Resource rationally using providing skill
Art guarantee.
A kind of device for purifying food-grade carbon-dioxide provided by the invention, including：
Pretreatment module, for being pre-processed to unstripped gas, obtain the first logistics；
Adsorption module, for carrying out adsorption treatment to first logistics, obtain the second logistics；
Liquefy module, for second logistics to be carried out into liquefaction processing, obtains third―party logistics；
Module is purified, for the third―party logistics to be purified, obtains food-grade carbon-dioxide.
In a kind of specific embodiment, the pretreatment module includes surge tank and the outlet with the surge tank
First compressor of line connection.
In a kind of specific embodiment, the adsorption module includes：For carrying out desulfurization process to first logistics
Desulfurization unit, and the logistics for being exported to the desulfurization unit removed water remove water unit.
In a kind of specific embodiment, the desulfurization unit includes：
The pre- desulfurizing tower that input is connected with the output end pipeline of first compressor；And
The hydrolysis tower that input is connected with the output end pipeline of the pre- desulfurizing tower；And
The fine de-sulfur tower that input is connected with the output end pipeline of the hydrolysis tower.
In a kind of specific embodiment, the output end pipeline that input and the desulfurization unit are included except water unit
The drying tower of connection and the second compressor for being connected to the drying tower port of export.
In a kind of specific embodiment, the purification module includes purifying column, reboiler, choke valve and gas-liquid separation
Device；The output end of the liquefaction module is connected with the upper input pipeline of the purifying column, the bottom rectifying of the purifying column
Tower output end is connected with the low-temperature receiver input pipeline of the reboiler, low-temperature receiver output end and the purifying column of the reboiler
Rectifying column input pipeline connects；The thermal source inlet of the reboiler is connected with the output end pipeline of the adsorption module, described
The thermal source inlet of reboiler is connected to the thermal source outlet of reboiler, the heat of the reboiler inside the reboiler by pipeline
Source exports to be connected with the liquefaction module pipeline；The outlet at bottom of the reboiler connects the choke valve by pipeline and inputted
End, the choke valve output end connect the top input of the gas-liquid separator by pipeline.
In a kind of specific embodiment, the liquefaction module includes working medium carbon dioxide precooling device and ammonia cooler；It is described
The input of working medium carbon dioxide precooling device is connected with the output end pipeline of the adsorption module, the working medium carbon dioxide precooling
The output end of device is connected with the input pipeline of the ammonia cooler；The gas output end of the reboiler is defeated with the ammonia cooler
Enter the connection of end pipe line；The output end of the ammonia cooler is connected with the upper input pipeline of the purifying column.
In a kind of specific embodiment, the top gas outlet of the gas-liquid separator is connected to described carry by pipeline
The cold doubtful device entrance in top of pure tower；The top gas outlet of the gas-liquid separator also first passes through the top of pipeline and the purifying column
The low-temperature receiver entrance of the working medium carbon dioxide precooling device is connected to after portion's fixed gas outlet connection.
The present invention also provides a kind of method for purifying food-grade carbon-dioxide, comprises the following steps：
Unstripped gas is pre-processed, obtains the first logistics；
First logistics is subjected to adsorption treatment, obtains the second logistics；
Second logistics is subjected to liquefaction processing, obtains third―party logistics；
The third―party logistics are purified, obtain food-grade carbon-dioxide.
It is described to be pre-processed unstripped gas in a kind of specific embodiment, the first logistics is obtained, including：
By surge tank by the unstripped gas voltage stabilizing；
Unstripped gas after voltage stabilizing is inputted into the first compressor and carries out one stage of compression, obtains pressure as the of the first predetermined pressure
One logistics；
First logistics is cooled to normal temperature.
It is described that first logistics is subjected to adsorption treatment in a kind of specific embodiment, the second logistics is obtained, is wrapped
Include：
H in first logistics is removed by pre- desulfurizing tower2S, obtain the 4th logistics；
COS in 4th logistics is hydrolyzed to by H by hydrolysis tower2S and CO2, obtain the 5th logistics；
5th logistics input fine de-sulfur tower is sloughed into H2S, obtain the 6th logistics that total sulfur content is less than first threshold；
Drying tower will be inputted after 6th operating mode pattern to normal temperature, removed by the drying tower in the 6th logistics
Moisture and methanol, obtain the 7th logistics that moisture is less than the 3rd threshold value less than Second Threshold and methanol content；
By the second compressor by the 7th logistics multi-stage compression to the second predetermined pressure, the second logistics is obtained.
It is described to purify the third―party logistics in a kind of specific embodiment, food-grade carbon-dioxide is obtained, including：
By third―party logistics input purifying column purification, the bottom rectifying column that the 8th logistics enters the purifying column is obtained；
The 9th logistics input reboiler heating that the rectifying column is exported, obtains the tenth logistics and re-enters the rectifying
Tower, while obtain the 11st logistics and exported from the outlet at bottom of the reboiler；
11st logistics is exported to choke valve, throttled through the choke valve to the 3rd predetermined pressure；
The 12nd logistics input gas-liquid separator that the choke valve is exported carries out gas-liquid separation；
Food-grade carbon-dioxide output is obtained after the gas-liquid separator bottom liquid is cooled down.
It is described that second logistics is subjected to liquefaction processing in a kind of specific embodiment, third―party logistics are obtained, are wrapped
Include：
Second logistics is divided into two parts, portion is sent into working medium carbon dioxide precooling device and cooled down, another feeding
9th logistics of the reboiler and rectifying column input reboiler carries out heat exchange and obtains cold；
By the 13rd logistics of working medium carbon dioxide precooling device output and the 14th logistics of reboiler output
Common ammonia cooler of being sent into is cooled down, third―party logistics described in ammonia cooler final output.
In a kind of specific embodiment, in addition to：
The top gas of the gas-liquid separator is exported to the purifying column evaporator overhead condenser as the step of cold fluid；
And
The top fixed gas of the top gas of the gas-liquid separator and the purifying column is exported to the working medium dioxy
The step of cold source of the mdi prepolymer cooler as the working medium carbon dioxide.
The scheme of purification food-grade carbon-dioxide provided by the invention, after being pre-processed to unstripped gas, enters successively
The processes such as row desulfurization, water removal, liquefaction, purification, the impurity in coal gasification apparatus discharge carbon dioxide can be effectively removed, obtains purity
Food-grade carbon-dioxide higher than 99.999%.Device provided by the invention is reliable and stable, and relative energy consumption is small, and cost is low, yield
Up to 250,000 tons/year, with coal gasification caused by carbon dioxide air source match, effectively can remove in food-class liquid CO 2
Harmful substance, the food-grade carbon-dioxide of production have safety guarantee.In addition, scheme provided by the invention can make full use of system
Waste heat and waste cold, reduce the operating cost of liquefaction workshop section.
Brief description of the drawings
Fig. 1 is a kind of apparatus structure schematic diagram for purifying food-grade carbon-dioxide provided in an embodiment of the present invention；
Fig. 2 is a kind of method flow diagram for purifying food-grade carbon-dioxide provided in an embodiment of the present invention；
Fig. 3 is step S2 flow chart；
Fig. 4 is step S4 flow chart；
Fig. 5 is the apparatus structure schematic diagram for the purification food-grade carbon-dioxide that the embodiment of the present invention one provides.
[description of reference numerals]
101st, pretreatment module, 102, adsorption module, 103, liquefaction module, 104, purification module,
1st, unstripped gas, 2, surge tank outlet streams, the 3, first logistics, the 4, the 4th logistics,
5th, the 5th logistics, the 6, the 6th logistics, the 7, the 7th logistics, the 8, second logistics,
9th, the 15th logistics, the 10, the 16th logistics, the 11, the 13rd logistics, the 12, the 14th logistics,
13rd, the 17th logistics, 14, third―party logistics, the 15, the 9th logistics, the 16, the 11st logistics,
17th, food-grade carbon-dioxide, 18, gas-liquid separator top gas, the 19, first cold fluid,
20th, purification column overhead fixed gas, the 21, second cold fluid, the 22, the tenth logistics,
23rd, carbon dioxide 24, precooling carbon dioxide outlet 25, gas ammonia are vaporized,
V-01, surge tank, C-01, pre- desulfurizing tower, C-02, hydrolysis tower, C-03, fine de-sulfur tower,
C-04, drying tower, E-01, working medium carbon dioxide precooling device, E-02, ammonia cooler,
E-03, reboiler, C-05, purifying column, V-02, gas-liquid separator.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing and tool
Body embodiment is described in detail.
Fig. 1 is the structural representation of the device of purification food-grade carbon-dioxide provided in an embodiment of the present invention, such as institute in Fig. 1
Show, the device includes pretreatment module 101, adsorption module 102, liquefaction module 103 and purification module 104；Wherein, mould is pre-processed
Block 101, for being pre-processed to unstripped gas, obtain the first logistics；Adsorption module 102, for being carried out to first logistics
Adsorption treatment, obtain the second logistics；Liquefy module 103, for second logistics to be carried out into liquefaction processing, obtains the 3rd thing
Stream；Module 104 is purified, for the third―party logistics to be purified, obtains food-grade carbon-dioxide, in addition, purification module 104 produces
Waste heat and waste cold be also transmitted back to liquefaction module 103 carry out secondary use, reduce liquefaction workshop section operating cost.
In the present embodiment, after being pre-processed to unstripped gas, the works such as desulfurization, water removal, liquefaction, purification are carried out successively
Sequence, the impurity in coal gasification apparatus discharge carbon dioxide can be effectively removed, obtains the food-grade dioxy that purity is higher than 99.999%
Change carbon, device is reliable and stable, and relative energy consumption is small, and cost is low.
In a specific embodiment, pretreatment module 101 can include surge tank and the outlet with the surge tank
First compressor of pipeline connection.The buffered tank voltage stabilizing of unstripped gas, remove in medium after liquid, into compressor one stage of compression,
Gas pressure reaches 0.3~0.5MPa after compression, enters absorption workshop section after being cooled to normal temperature.
In a specific embodiment, adsorption module 102 can include desulfurization unit and except water unit；Wherein, desulfurization list
Member is used to carry out desulfurization process to first logistics；Removed water except water unit is used for the logistics to desulfurization unit output.
Preferably, desulfurization unit can include：Input is connected pre- de- with the output end pipeline of first compressor
Sulphur tower；And the hydrolysis tower that input is connected with the output end pipeline of the pre- desulfurizing tower；And input and the hydrolysis tower
Output end pipeline connection fine de-sulfur tower.First logistics first passes through pre- desulfurizing tower and removes H2S, subsequently into hydrolysis tower, hydrolysis
COS is hydrolyzed to H by tower2S and CO2Afterwards H is sloughed into fine de-sulfur tower2S, the total sulfur content of logistics is set to be less than 0.1ppm, temperature control
Enter follow-up de-watering stage after normal temperature.
Preferably, except water unit includes the drying tower of the output end pipeline connection of input and desulfurization unit and is connected to
Second compressor of the drying tower port of export.The logistics of desulfurization unit output enters drying tower, while removes water and methanol.Water content
It is down to below 20ppm；Methanol content enters compressor set after being down to below 10ppm, through multi-stage compression to 2.5~3.5MPa, enters
Enter workshop section of liquefying.
In a specific embodiment, purifying column, reboiler, choke valve, gas-liquid separator can be included by purifying module 104
And storage tank；Wherein, the output end for the module 103 that liquefies and the upper input pipeline of purifying column connect, the bottom rectifying of purifying column
The low-temperature receiver input pipeline of tower output end and reboiler connects, the low-temperature receiver output end of reboiler and the rectifying column input of purifying column
Pipeline connects；The thermal source inlet of reboiler is connected with the output end pipeline of adsorption module 102, and the thermal source inlet of reboiler is boiling again
The thermal source outlet of reboiler is connected to inside device by pipeline, the thermal source outlet of reboiler is connected with the liquefaction pipeline of module 103；Again
The outlet at bottom for boiling device connects choke valve input by pipeline, and choke valve output end connects the top of gas-liquid separator by pipeline
Portion's input, the outlet at bottom of gas-liquid separator connect storage tank by pipeline.In the present embodiment, third―party logistics are entered with liquid to be carried
Pure tower, the liquid CO 2 containing a small amount of light component enters rectifier bottoms, light in unstripped gas after tower bottom reboiler heats
Component is exported to purifying column by the thermal source outlet of reboiler, then rises to tower top, in tower top partial condensation；And by purifying column
Liquid CO 2 of the purity higher than 99.99% for into the logistics of reboiler obtain after heat exchange is flowed by reboiler bottom
Go out, gas-liquid separator is entered after choke valve throttles to 2.2Mpa and carries out gas-liquid separation, after the cooling of gas-liquid separator bottom liquid
Stored for food-grade carbon-dioxide into storage tank.
In a specific embodiment, liquefaction module 103 may include working medium carbon dioxide precooling device and ammonia cooler；Working medium two
The input of carbonoxide forecooler is connected with the output end pipeline of adsorption module 102, the output end of working medium carbon dioxide precooling device
It is connected with the input pipeline of ammonia cooler；The gas output end of reboiler and the input pipeline of ammonia cooler connect；Ammonia cooler
The upper input pipeline of output end and purifying column connects.It is so designed that, the part hot gas input that adsorption module 102 is exported is again
The logistics heating that device is used to input rectifier bottoms reboiler is boiled, while has reached the second thing exported to adsorption module 102
The part cooling effect of stream, takes full advantage of system waste heat, improves energy utilization rate.
In a specific embodiment, the top gas outlet of gas-liquid separator is connected to the top of purifying column by pipeline
Cold doubtful device entrance, using the cold fluid as cold doubtful device；The top gas outlet of gas-liquid separator also first passes through pipeline and purifying column
Top fixed gas outlet connection after be connected to the low-temperature receiver entrance of working medium carbon dioxide precooling device, using pre- as working medium carbon dioxide
The low-temperature receiver of cooler.The present embodiment, the residual air cold of gas-liquid separator is further make use of, reduce further the fortune of liquefaction workshop section
Row cost.
Corresponding to the device of purification food-grade carbon-dioxide provided in an embodiment of the present invention, the embodiment of the present invention also provides one
The method of kind purification food-grade carbon-dioxide.
Fig. 2 show a kind of method flow diagram for purifying food-grade carbon-dioxide provided in an embodiment of the present invention, in Fig. 2
Shown, this method comprises the following steps：
S1：Unstripped gas is pre-processed, obtains the first logistics.
Preferably, step S1 can first pass through surge tank by unstripped gas voltage stabilizing, then by the unstripped gas input first after voltage stabilizing
Compressor carries out one stage of compression, obtains the first logistics that pressure is the first predetermined pressure；The first logistics is finally cooled to normal temperature
Absorption process can be entered.
S2：First logistics is subjected to adsorption treatment, obtains the second logistics.
In the present embodiment, the first logistics is subjected to the adsorption treatment such as desulfurization and water removal, it is higher to obtain carbon dioxide content
Second logistics.
Preferably, as shown in figure 3, step S2 may comprise steps of S21-S25：
S21：H in first logistics is removed by pre- desulfurizing tower2S, obtain the 4th logistics；
S22：COS in 4th logistics is hydrolyzed to by H by hydrolysis tower2S and CO2, obtain the 5th logistics；
S23：5th logistics input fine de-sulfur tower is sloughed into H2S, obtain the 6th logistics that total sulfur content is less than first threshold；
S24：Drying tower will be inputted after 6th operating mode pattern to normal temperature, by drying tower remove the 6th logistics in moisture and
Methanol, obtain the 7th logistics that moisture is less than the 3rd threshold value less than Second Threshold and methanol content；
S25：By the second compressor by the 7th logistics multi-stage compression to the second predetermined pressure, the second logistics is obtained.
S3：Second logistics is subjected to liquefaction processing, obtains third―party logistics.
In the present embodiment, the second logistics (the higher gas of carbon dioxide content) is subjected to liquefaction processing, obtains titanium dioxide
The higher liquid of carbon content is as third―party logistics.
S4：Third―party logistics are purified, obtain food-grade carbon-dioxide.
In the present embodiment, the higher third―party logistics of carbon dioxide content are subjected to carbon dioxide purification, finally give food
Grade carbon-dioxide.
Preferably, as shown in figure 4, step S4 can be realized by following steps S41-S45：
S41：By third―party logistics input purifying column purification, the bottom rectifying column that the 8th logistics enters purifying column is obtained；
S42：By the 9th logistics input reboiler heating of rectifying column output, obtain the tenth logistics and re-enter rectifying column,
The 11st logistics is obtained simultaneously to export from the outlet at bottom of reboiler；
In this step, the 9th logistics of rectifying column output is the liquid CO 2 containing a small amount of light component, and rectifying column is defeated
After the 9th logistics gone out is heated by reboiler, the light component in unstripped gas is recycled to purifying column, then rises to tower top, in tower
Top is condensed, and liquid CO 2 of the purity higher than 99.99% is then flowed out as the 11st logistics by reboiler bottom.
S43：11st logistics is exported to choke valve, throttled through choke valve to the 3rd predetermined pressure；
S44：The 12nd logistics input gas-liquid separator of choke valve output is subjected to gas-liquid separation；
S45：Food-grade carbon-dioxide output is obtained after gas-liquid separator bottom liquid is cooled down.
Method provided by the invention, after being pre-processed to unstripped gas, desulfurization, water removal, liquefaction, purification are carried out successively
Etc. process, the impurity in coal gasification apparatus discharge carbon dioxide can be effectively removed, obtains the food-grade that purity is higher than 99.999%
Carbon dioxide.Device provided by the invention is reliable and stable, and relative energy consumption is small, and cost is low, and yield is up to 250,000 tons/year, with coal gas
Carbon dioxide air source caused by change matches, and can effectively remove the harmful substance in food-class liquid CO 2, the food of production
Grade carbon-dioxide has safety guarantee.
In another preferred embodiment, step S3 by the second logistics carry out liquefy processing method can be：First by
Two logistics are divided into two parts, and portion is sent into working medium carbon dioxide precooling device and cooled down, and another is sent into reboiler and rectifying column is defeated
The 9th logistics for entering reboiler carries out heat exchange acquisition cold；The 13rd logistics that then working medium carbon dioxide precooling device is exported
The 14th logistics with reboiler output is sent into ammonia cooler and cooled down jointly, ammonia cooler final output third―party logistics.This implementation
In example, the second logistics of part hot gas is inputted into nineth logistics of the reboiler to rectifier bottoms input reboiler and heated, is reached simultaneously
The part cooling effect to the second logistics has been arrived, system waste heat has been taken full advantage of, improves energy utilization rate.
Further, in another preferred embodiment, method provided by the invention may also include：By the top of gas-liquid separator
Portion's gas export to purifying column evaporator overhead condenser as cold fluid the step of；And by the top gas of gas-liquid separator and purification
The step of top fixed gas of tower is exported to cold source of the working medium carbon dioxide precooling device as working medium carbon dioxide.This implementation
Example, further make use of the residual air cold of gas-liquid separator, reduce further the operating cost of liquefaction workshop section.
Illustrate below by specific embodiment it is provided in an embodiment of the present invention purification food-grade carbon-dioxide device and
Method.
Embodiment one
Fig. 5 is the apparatus structure schematic diagram for the purification food-grade carbon-dioxide that the embodiment of the present invention one provides, such as Fig. 5 institutes
Show, the device of the present embodiment includes：Surge tank V-01, pre- desulfurizing tower C-01, hydrolysis tower C-02, fine de-sulfur tower C-03, drying tower
C-04, working medium carbon dioxide precooling device E-01, ammonia cooler E-02, reboiler E-03, purifying column C-05, gas-liquid separator V-02,
The choke valve not represented in first compressor, the second compressor and figure.Wherein, unstripped gas is defeated from surge tank V-01 input port
Enter, surge tank V-01 output end be sequentially connected the first compressor, pre- desulfurizing tower C-01, hydrolysis tower C-02, fine de-sulfur tower C-03,
Drying tower C-04；Drying tower C-04 output end is respectively connecting to working medium carbon dioxide precooling device E-01 input by pipeline
And reboiler E-03 thermal source inlet, working medium carbon dioxide precooling device E-01 output end and reboiler E-03 thermal source go out
Mouth is connected to ammonia cooler E-02 input, and ammonia cooler E-02 output end connects with purifying column C-05 upper input pipeline
Connect；Purifying column C-05 bottoms rectifying column output end is connected with reboiler E-03 low-temperature receiver input, and reboiler E-03 low-temperature receiver is defeated
Go out the rectifying column input that the end right side connects back to purifying column C-05, form a circulation loop；Reboiler E-03 outlet at bottom leads to
Pipeline connection choke valve input is crossed, choke valve output end connects gas-liquid separator V-02 top input by pipeline, most
The food-grade carbon-dioxide obtained eventually exports from gas-liquid separator V-02.Further, as shown in Figure 2, gas-liquid separator V-
02 top gas outlet is connected to the purifying column C-05 cold doubtful device entrance in top, gas-liquid separator V-02 top gas outlet
Pipeline is also first passed through with being connected to working medium carbon dioxide precooling device E-01's after purifying column C-05 top fixed gas outlet connection
Low-temperature receiver entrance.
In one embodiment, if the temperature of unstripped gas 1 is 30 DEG C, pressure 0.04MPaG, flow 19.2kNm3/ h,
The each component concentration of unstripped gas 1 is respectively：CO2：98.5%vol, CO：0.07%, H2：0.08%, N2：0.32%, CH4：
0.00049%, CH3OH：0.02%, H2S：0.13%, COS：0.07%, Ar：0.0004%, then using Fig. 5 shown devices and
Methods For Purification food-grade carbon-dioxide provided by the invention, comprises the following steps：
(1) the buffered tank V-01 voltage stabilizings of unstripped gas 1, surge tank V-01 outlet streams 2 are entered into the first compressor compresses
To 0.3MPa, because the temperature of gas increases with pressure and raise, therefore the logistics after compression carries cooler drop through compressor
After warm to 40 DEG C, obtain the first logistics 3 and enter absorption process.
(2) first logistics 3 enter pre- desulfurizing tower C-01 and remove most of H2After S, the 4th thing of pre- desulfurizing tower C-01 outputs
Stream 4 enters hydrolysis tower C-02, and hydrolysis occurs, and the COS in the 4th logistics 4 is hydrolyzed to H2S and CO2；Hydrolysis tower C-02 outputs
5th logistics 5 enters fine de-sulfur tower C-03, removes remaining H2Total sulfur content drops in 6th logistics 6 of S, fine de-sulfur tower C-03 output
To 0.06ppm；After drying tower C-04 dryings, the water content of the 7th logistics 7 of drying tower C-04 outputs is down to for 6th logistics 6
7ppm, methanol content are down to 2ppm.7th logistics 7 enters the second compressor and cooled down respectively through 1.1MPa and 2.5MPa two stages of compression
Afterwards, the second logistics 8 of the second compressor output with pressure 2.5MPa, 40 DEG C of temperature operating mode under enter follow-up cooling workshop section.
A part (the 15th logistics 9 shown in Fig. 5) for second logistics 8 of (3) second compressors output enters working medium two
Precooling (being controlled by the regulating valve A in Fig. 5) in carbonoxide forecooler E-01, is cooled to -8 DEG C and is sent into ammonia cooler E-02.Second pressure
Contracting machine output the second logistics 8 another part (the 16th logistics 10 shown in Fig. 5) enter reboiler E-03 as thermal source (by
Regulating valve B is controlled), heating purifying column C-05 rectifier bottoms export the 9th logistics 15, and obtain cold, and temperature is down to -11
DEG C, it is same to be sent into ammonia cooler E-02, i.e. the 13rd logistics 11 and reboiler E-03 of working medium carbon dioxide precooling device E-01 outputs
14th logistics 12 of output converges is sent into ammonia cooler E-02 for the 17th logistics 13 shown in Fig. 5.
(4) the 17th logistics 13 is cooled to -18 DEG C by ammonia cooler E-02, now ammonia cooler E-02 export third―party logistics 14 with
Liquid enters purifying column C-05, and the liquid CO 2 (i.e. the 8th logistics) containing a small amount of light component enters rectifier bottoms, through tower
After bottom exports the 9th logistics 15 to reboiler E-03 heating, the light component in unstripped gas is sent back to purification as the tenth logistics 22
Tower, the tenth logistics 22 rise to tower top, and in tower top partial condensation, fixed gas enters working medium carbon dioxide precooling device E-01 as cold
Source, and liquid CO 2 of the purity higher than 99.99% is flowed out as the 11st logistics 16 by reboiler E-01 bottoms, through throttling
Valve enters gas-liquid separator V-02 after throttling to 2.2Mpa the 12nd logistics.
(5) temperature of gas-liquid separator V-02 top gas 18 is -16 DEG C, this part of portion gas 18 output to purification
For tower C-05 evaporator overhead condensers as the first cold fluid 19, it is cold that another part with purifying column C-05 tower tops fixed gas 20 is mixed into second
Fluid 21, the second cold fluid 21 enter working medium carbon dioxide precooling device E-01 as low-temperature receiver.Gas-liquid separator V-02 bottom liquids
Exported after cooling as food-grade carbon-dioxide 17, such as exportable value storage tank storage.
The present embodiment one can effectively remove the impurity in Coal Gasification Technology discharge carbon dioxide, obtain purity and be higher than
99.999% food-grade carbon-dioxide, and the waste heat and waste cold of system are made full use of, reduce the operating cost of liquefaction workshop section.
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (14)
- A kind of 1. device for purifying food-grade carbon-dioxide, it is characterised in that including：Pretreatment module, for being pre-processed to unstripped gas, obtain the first logistics；Adsorption module, for carrying out adsorption treatment to first logistics, obtain the second logistics；Liquefy module, for second logistics to be carried out into liquefaction processing, obtains third―party logistics；Module is purified, for the third―party logistics to be purified, obtains food-grade carbon-dioxide.
- 2. the device of purification food-grade carbon-dioxide as claimed in claim 1, it is characterised in that the pretreatment module includes Surge tank and the first compressor being connected with the outlet line of the surge tank.
- 3. the device of purification food-grade carbon-dioxide as claimed in claim 1, it is characterised in that the adsorption module includes： For carrying out the desulfurization unit of desulfurization process to first logistics, and the logistics for being exported to the desulfurization unit is carried out Water removal removes water unit.
- 4. the device of purification food-grade carbon-dioxide as claimed in claim 3, it is characterised in that the desulfurization unit includes：The pre- desulfurizing tower that input is connected with the output end pipeline of first compressor；AndThe hydrolysis tower that input is connected with the output end pipeline of the pre- desulfurizing tower；AndThe fine de-sulfur tower that input is connected with the output end pipeline of the hydrolysis tower.
- 5. the device of the purification food-grade carbon-dioxide as described in claim 3 or 4, it is characterised in that described to remove water unit bag Include drying tower that input is connected with the output end pipeline of the desulfurization unit and be connected to the of the drying tower port of export Two compressors.
- 6. the device of purification food-grade carbon-dioxide as claimed in claim 1, it is characterised in that the purification module includes carrying Pure tower, reboiler, choke valve and gas-liquid separator；The output end and the upper input pipe of the purifying column of the liquefaction module Line is connected, and the bottom rectifying column output end of the purifying column is connected with the low-temperature receiver input pipeline of the reboiler, described to boil again The low-temperature receiver output end of device is connected with the rectifying column input pipeline of the purifying column；The thermal source inlet of the reboiler and the suction The output end pipeline connection of attached module, the thermal source inlet of the reboiler is connected to inside the reboiler by pipeline to boil again The thermal source outlet of device, the thermal source outlet of the reboiler are connected with the liquefaction module pipeline；The outlet at bottom of the reboiler The choke valve input is connected by pipeline, the choke valve output end connects the top of the gas-liquid separator by pipeline Input.
- 7. the device of purification food-grade carbon-dioxide as claimed in claim 6, it is characterised in that the liquefaction module includes work Matter carbon dioxide precooling device and ammonia cooler；The input of the working medium carbon dioxide precooling device and the output end of the adsorption module Pipeline is connected, and the output end of the working medium carbon dioxide precooling device is connected with the input pipeline of the ammonia cooler；It is described to boil again The gas output end of device is connected with the input pipeline of the ammonia cooler；The output end of the ammonia cooler is upper with the purifying column Portion's input pipeline connection.
- 8. the device of purification food-grade carbon-dioxide as claimed in claim 7, it is characterised in that the top of the gas-liquid separator Portion's gas vent is connected to the cold doubtful device entrance in top of the purifying column by pipeline；The top gas of the gas-liquid separator goes out Mouth also first passes through pipeline with being connected to the working medium carbon dioxide precooling device after the top fixed gas outlet connection of the purifying column Low-temperature receiver entrance.
- A kind of 9. method for purifying food-grade carbon-dioxide, it is characterised in that comprise the following steps：Unstripped gas is pre-processed, obtains the first logistics；First logistics is subjected to adsorption treatment, obtains the second logistics；Second logistics is subjected to liquefaction processing, obtains third―party logistics；The third―party logistics are purified, obtain food-grade carbon-dioxide.
- 10. the method for purification food-grade carbon-dioxide as claimed in claim 9, it is characterised in that described to carry out unstripped gas Pretreatment, obtains the first logistics, including：By surge tank by the unstripped gas voltage stabilizing；Unstripped gas after voltage stabilizing is inputted into the first compressor and carries out one stage of compression, obtains the first thing that pressure is the first predetermined pressure Stream；First logistics is cooled to normal temperature.
- 11. the method for purification food-grade carbon-dioxide as claimed in claim 9, it is characterised in that described by first thing Stream carries out adsorption treatment, obtains the second logistics, including：H in first logistics is removed by pre- desulfurizing tower2S, obtain the 4th logistics；COS in 4th logistics is hydrolyzed to by H by hydrolysis tower2S and CO2, obtain the 5th logistics；5th logistics input fine de-sulfur tower is sloughed into H2S, obtain the 6th logistics that total sulfur content is less than first threshold；Drying tower will be inputted after 6th operating mode pattern to normal temperature, the water in the 6th logistics is removed by the drying tower Point and methanol, obtain the 7th logistics that moisture is less than the 3rd threshold value less than Second Threshold and methanol content；By the second compressor by the 7th logistics multi-stage compression to the second predetermined pressure, the second logistics is obtained.
- 12. the method for purification food-grade carbon-dioxide as claimed in claim 9, it is characterised in that described by the 3rd thing Stream purification, obtains food-grade carbon-dioxide, including：By third―party logistics input purifying column purification, the bottom rectifying column that the 8th logistics enters the purifying column is obtained；The 9th logistics input reboiler heating that the rectifying column is exported, obtains the tenth logistics and re-enters the rectifying column, The 11st logistics is obtained simultaneously to export from the outlet at bottom of the reboiler；11st logistics is exported to choke valve, throttled through the choke valve to the 3rd predetermined pressure；The 12nd logistics input gas-liquid separator that the choke valve is exported carries out gas-liquid separation；Food-grade carbon-dioxide output is obtained after the gas-liquid separator bottom liquid is cooled down.
- 13. the method for purification food-grade carbon-dioxide as claimed in claim 12, it is characterised in that described by second thing Stream carries out liquefaction processing, obtains third―party logistics, including：Second logistics is divided into two parts, portion is sent into working medium carbon dioxide precooling device and cooled down, described in another feeding 9th logistics of reboiler and rectifying column input reboiler carries out heat exchange and obtains cold；14th logistics of the 13rd logistics of working medium carbon dioxide precooling device output and reboiler output is common It is sent into ammonia cooler to be cooled down, third―party logistics described in ammonia cooler final output.
- 14. the method for purification food-grade carbon-dioxide as claimed in claim 13, it is characterised in that also include：The top gas of the gas-liquid separator is exported to the purifying column evaporator overhead condenser as the step of cold fluid；AndThe top fixed gas of the top gas of the gas-liquid separator and the purifying column is exported to the working medium carbon dioxide The step of cold source of the forecooler as the working medium carbon dioxide.
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| CN110015664A (en) * | 2019-04-24 | 2019-07-16 | 华东能源环保股份有限公司 | A kind of efficient purification system of food-grade carbon-dioxide and its technique |
| CN111453747A (en) * | 2020-04-08 | 2020-07-28 | 河北云瑞化工设备有限公司 | Device for preparing battery-grade lithium carbonate from crude lithium carbonate and using method of device |
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