CN108569698A - A kind of carbon dioxide purification device - Google Patents
A kind of carbon dioxide purification device Download PDFInfo
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- CN108569698A CN108569698A CN201710558139.1A CN201710558139A CN108569698A CN 108569698 A CN108569698 A CN 108569698A CN 201710558139 A CN201710558139 A CN 201710558139A CN 108569698 A CN108569698 A CN 108569698A
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- column
- carbon dioxide
- rectifying column
- molecular sieve
- condenser
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 65
- 239000003507 refrigerant Substances 0.000 claims abstract description 35
- 239000003463 adsorbent Substances 0.000 claims abstract description 33
- 238000007710 freezing Methods 0.000 claims abstract description 22
- 230000008014 freezing Effects 0.000 claims abstract description 22
- 239000012530 fluid Substances 0.000 claims abstract description 15
- 239000006200 vaporizer Substances 0.000 claims abstract description 13
- 230000017105 transposition Effects 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 63
- 239000002808 molecular sieve Substances 0.000 claims description 42
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 42
- 229960004424 carbon dioxide Drugs 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 239000010457 zeolite Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006477 desulfuration reaction Methods 0.000 claims description 13
- 230000023556 desulfurization Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011240 wet gel Substances 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002826 coolant Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 description 20
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- -1 nitrogenous compound Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
The invention belongs to gas purification technical fields.The invention discloses a kind of carbon dioxide purifying devices comprising fluid reservoir, vaporizer, adsorption column group, liquefaction plate change, rectifying column, condenser, reboiler and freezing unit；Fluid reservoir, vaporizer, adsorption column group pass sequentially through gas pipeline with rectifying column and connect, and condenser is located above rectifying column, and reboiler is connected with rectifying column and is located at the lower section of rectifying column；Plate transposition liquefy between adsorption column group and rectifying column；Freezing unit is connected by refrigerant inlet pipe and refrigerant return line with condenser.The adsorbent/catalyst used in the present invention has higher absorption/catalytic efficiency, disclosure satisfy that the requirement of production efficiency；Coolant can be fully utilized in the present invention, and air-discharging can be used for the precooling of unstripped gas when needed, realize making full use of for resource, can reduce energy consumption；The high-purity carbon dioxide of 99.999% or even 99.9995% purity can be obtained by being handled through this purification devices.
Description
Technical field
The present invention relates to gas purification technical fields, more particularly, to a kind of carbon dioxide purification device.
Background technology
Carbon dioxide is a kind of colourless, tasteless, nontoxic, nonflammable gas, gas density 1.976kg/m3, liquid is close
Spend 929.5kg/m3, molecular weight 44.01,31.4 DEG C, critical pressure 7.28MPa of critical-temperature, atmospheric carbon dioxide it is pressurized or
It can directly be liquefied when cooling, Solid dry ice can be obtained when carbon dioxide is depressurized throttling, Solid dry ice directly distils can
Atmospheric carbon dioxide is generated, is 0.518mpa in pressure, temperature is at -56.6 °C, gas, liquid, solid three-phase coexistence.
Although carbon dioxide is well known to the public by the greenhouse gases as influence weather, carbon dioxide is also one
Kind important carbon resource is widely used in chemical industry, machinery, food, medical and agriculture etc. multiple fields, it is total also to have become people
The research topic for being.
In order to meet the requirement that above-mentioned field uses carbon dioxide, carbon dioxide must it is purified to 99.99% and with
On.Chinese patent notification number CN106430194A, authorized announcement date are on 2 22nd, 2017, disclose an entitled Gaochun two
Liquefier, catalytic bed, adsorbent bed, precooling are passed through in the patent of invention of carbonoxide equipment for purifying, carbon dioxide purification channel successively
Device finally connects rectifying column, the invention by carbon dioxide catalysis oxidation purifying carbon dioxide by adsorption distillation technology, but its
There is also larger problem, catalytic oxidation process can cause catalytic bed operating pressure excessive, cause before adsorption process
Catalyst amount increases, and also results in whole refining effect and is deteriorated, and is in addition first catalyzed adsorption treatment process again it is also possible to occurring
Situations such as raw material certain impurity therein cause catalyst poisoning so that refining effect is deteriorated.
Invention content
To solve the above problems, the present invention provides a kind of purification process rationally, purification efficiency is higher, cost is relatively low, tool
There is the carbon dioxide purifying device of good refining effect, 99.999% or even 99.9995% or more can be made through the invention
The carbon dioxide of purity.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of carbon dioxide purification device comprising fluid reservoir, vaporizer, adsorption column group, liquefaction plate change, rectifying column, condenser,
Reboiler and freezing unit；Fluid reservoir, vaporizer, adsorption column group pass sequentially through gas pipeline with rectifying column and connect, condenser position
Above rectifying column, the evacuated tube of rectifying column passes through condenser, and reboiler is connected with rectifying column and is located at the lower section of rectifying column,
Heater is additionally provided in reboiler；Plate transposition liquefy between adsorption column group and rectifying column, gas pipeline passes through liquefaction plate to change；It is cold
Freeze unit be connected with condenser by refrigerant inlet pipe and refrigerant return line, freezing unit refrigerant inlet pipe and refrigerant return line it
Between be additionally provided with refrigerant siphunculus, refrigerant siphunculus passes through liquefaction plate to change.
The present invention mainly takes two kinds of techniques of absorption and rectifying to remove the impurity in CO 2 raw material gas, these impurity packets
Include but be not limited to water, sulfur compound impurities, nitrogenous compound impurity, hydrocarbon impurities, alcohol aldehyde impurity and some light component impurity
Deng.Unstripped gas is stored in fluid reservoir in fluid form, when purifying, gasifier is first passed through, then along flue
Road enters in adsorption column group, passes through 4 adsorption columns successively and removes corresponding impurity, the first two adsorption column is mainly inhaled using physics
Subsidiary formula formula removes impurity, and gas is heated to 100~140 DEG C and is removed in favor of the absorption of sorbing material in the two adsorption columns
Miscellaneous, latter two adsorption column is mainly the impurity or carbon dioxide for becoming corresponding impurity to be easy to absorption in the way of catalysis,
Recycle the porous molecular screen carrier of catalyst by impurity absorption, gas is heated to 200~260 DEG C in latter two adsorption column
To adapt to the catalytic temperature of catalyst, while needing timely and appropriate discovery by oxygen to meet wanting for catalysis in latter two adsorption column
It asks；Gas after adsorption treatment is changed through the plate that liquefies（Temperature is -22 DEG C or so）Heat exchange is carried out, enters rectifying after completing cooling
It is specifically the medium position into rectifying column in tower, the condenser temperature at the top of rectifying column is set as -24 DEG C or so, essence
Evaporate having heaters in the reboiler of tower bottom, heater（Heater setpoint temperatures are -19 DEG C or so）Gas is heated, is steamed
Rise upward relatively hot phase hands over matter, light component impurity to be detached and be discharged by evacuated tube with the colder liquid phase at the top of rectifying column；
Liquid phase after rectifying in reboiler just reaches purity requirement.
It is changed preferably, carbon dioxide purification device is additionally provided with compensating plate, compensating plate transposition is changed and adsorption column in liquefaction plate
Between group, gas conduit passes therethrough, and the evacuated tube of rectifying column also passes therethrough.
In compensating plate changes, heat exchange first is carried out to the gas after adsorption cleaning using the low temperature air-discharging at the top of rectifying column
It is insufficient also to solve summer refrigerator refrigerating capacity to reduce the operating pressure for freezing unit under summer hot environment for precooling treatment
The problem of；It need not start in the case where refrigerator refrigerating capacity disclosure satisfy that, at this time low temperature air-discharging direct emission.
Preferably, being additionally provided with refrigerator temperature control galvanic couple in condenser, freezing unit is equipped with Control of Chiller case, freezing
Machine temperature control galvanic couple and the electrical connection of Control of Chiller case.
Refrigerator temperature control galvanic couple is located in condenser, detects the temperature in condenser, will detect temperature information and feed back to
Refrigerator word case, and control the refrigeration effect of refrigerator.
Preferably, there are four adsorption columns to form for adsorption column group, respectively desulfurization removing nitric column, dry column, de- hydrocarbon column and de-
Alcohol full gear column.
Preferably, desulfurization removing nitric column is equipped with the adsorbent being made of aluminium oxide, activated carbon and sodium hydroxide, dry column dress
By the drier being made of activated carbon and silica gel, takes off hydrocarbon column and copper silver adsorbent of molecular sieve is housed, dealcoholysis full gear column is equipped with by zeolite
The adsorbent of molecular sieve and vanadic anhydride composition.
Preferably, being respectively equipped with independent heating device outside four adsorption columns.
Respectively added with corresponding adsorbent to remove the impurity in unstripped gas in four adsorption columns in adsorption column group,
Middle desulfurization removing nitric column is mainly sulfur-containing impurities, nitrogen-containing impurity and the water passed through in pure physisorption unstripped gas with dry column,
De- hydrocarbon column and dealcoholysis full gear column be mainly removed by way of chemical catalysis and physical absorption alkane in unstripped gas, alkene,
The impurity such as aromatic hydrocarbon and alcohol aldehyde hydroxy-containing component, wherein desulfurization removing nitric column and dry column work in 100~140 DEG C of temperature ranges
Make, de- hydrocarbon column and dealcoholysis full gear column then work in 200~260 DEG C of temperature ranges.The present invention totally is used first to adsorb and is catalyzed again
The mode of absorption removes the impurity composition in unstripped gas, avoids in the prior art, is first catalyzed again adsorption treatment and easily makes in the process
At catalyst poisoning, the problem of catalyst pressure etc. slows down purification efficiency is aggravated, can be very fast and be efficiently completed adsoption catalysis
Etc. processes, purifying speed can be mentioned, reduce cost.
Preferably, carbon dioxide purification device is additionally provided with electric cabinet, with outside adsorption column heating device, reboiler and
Refrigerator group is electrically connected.
Preferably, copper silver adsorbent of molecular sieve is by there is the raw material of following parts by weight to be made：100 parts of zeolite molecular sieve,
13~18 parts of 10wt% silver nitrate solutions, 10~15 parts of 10wt% copper nitrate solutions, 1~3 part of citric acid, 10~30 parts of water.
Preferably, copper silver adsorbent of molecular sieve is made by following steps：Silver nitrate solution and copper nitrate solution are mixed
Mixed solution is made and mixed solution is heated to 80~100 DEG C, zeolite molecular sieve is added thereto, while citric acid being dissolved
Citric acid solution is made in Yu Shuizhong, and then citric acid solution is added slowly in mixed solution, in adding procedure with 60~
The rotating speed of 120rpm is stirred, and continues 3~5 hours obtained wet gels of stirring after the completion of addition, then by wet gel 120~
Dry gel powder is made after drying and crush in 150 DEG C, is finally sintered 2~6 hours under 550~600 DEG C but its atmosphere, after cooling
Copper silver adsorbent of molecular sieve is made.
Preferably, zeolite molecular sieve is calcining 30~40 points using preceding elder generation under 600~700 DEG C of high-temperature oxygen environment
Clock is put into the sodium nitrate solution of 0.1~0.5moml/L after being cooled to room temperature and is impregnated 20~30 minutes, then uses water
It is dried after rinsing 3~4 times for use.
Copper silver molecular sieve is the catalyst-sorbent that the impurity such as hydro carbons in unstripped gas are removed for catalytic adsorption, copper silver molecule
Nanometer copper-silver particle in sieve has higher catalytic activity, and more stablizes with its compound rear catalytic activity of molecular sieve,
It can adapt to broader working environment；Citric acid is a kind of good reducing agent, it can be restored after being mixed with cupric silver solution
In copper silver and form corresponding gel, will can obtain nanometer copper-silver particle after gel drying obtained calcining.
Preferably absorbing copper silver particles to be removed attached first by zeolite molecular sieve progress sodium processing in preparation process
The heavier cation in zeolite surface, make the cation of zeolite molecular sieve surface and inner surfaces of pores be all lighter sodium from
Son, in this way in preparation process, can occur heavy metal displacement, allow more copper silver ions be attached to zeolite molecular sieve surface and
The inner surface in duct, the catalytic efficiency during carbon dioxide purification.
Therefore, the invention has the advantages that：
（1）The adsorbent/catalyst used in the present invention has higher absorption/catalytic efficiency, disclosure satisfy that production efficiency
It is required that；
（2）Coolant can be fully utilized in the present invention, and air-discharging can be used for the precooling of unstripped gas when needed, real
Making full use of for resource is showed, energy consumption can be substantially reduced；
（3）The problems such as device sequence and treatment process are arranged rationally, can greatly reduce catalyst poisoning in the present invention；
（4）High-purity the two of 99.999% or even 99.9995% purity can be obtained by being handled by carbon dioxide purification device of the present invention
Carbonoxide.
Description of the drawings
Fig. 1 is the schematic diagram of carbon dioxide purification device of the present invention；
In figure：Fluid reservoir 1, vaporizer 2, adsorption column group 3, desulfurization removing nitric column 31, dry column 32, de- hydrocarbon column 33 and dealcoholysis full gear column
34, heating device 35, liquefaction plate changes 4, rectifying column 5, condenser 6, reboiler 7, and heater 71 freezes unit 8, refrigerant inlet pipe
81, refrigerant return line 82, refrigerant siphunculus 83, refrigerator temperature control galvanic couple 84, Control of Chiller case 85, gas pipeline 9, evacuated tube
10, compensating plate changes 11, electric cabinet 12.
Specific implementation mode
Technical scheme of the present invention is further described With reference to embodiment.
Obviously, the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on this
Embodiment in invention, all other reality obtained by those of ordinary skill in the art without making creative efforts
Example is applied, shall fall within the protection scope of the present invention.
Embodiment 1
As shown in Figure 1, a kind of carbon dioxide purification device comprising fluid reservoir 1, vaporizer 2, adsorption column group 3, liquefaction plate change 4,
Rectifying column 5, condenser 6, reboiler 7 and freezing unit 8；Fluid reservoir, vaporizer, adsorption column group and rectifying column pass sequentially through gas
Pipeline 9 connects；There are four adsorption columns to form for adsorption column group, respectively is desulfurization removing nitric column 31, dry column 32, de- 33 and of hydrocarbon column
Dealcoholysis full gear column 34, desulfurization removing nitric column are equipped with the adsorbent that is made of aluminium oxide, activated carbon and sodium hydroxide, dry column be equipped with by
The drier of activated carbon and silica gel composition takes off hydrocarbon column and copper silver adsorbent of molecular sieve is housed, and dealcoholysis full gear column is equipped with by zeolite molecules
The adsorbent of sieve and vanadic anhydride composition, four adsorption columns are respectively equipped with independent heating device 35 outside；Condenser is located at essence
It evaporates above tower, the evacuated tube 10 of rectifying column passes through condenser；Reboiler is connected with rectifying column and is located at the lower section of rectifying column, then
It is additionally provided with heater 71 in boiling device；Plate transposition liquefy between adsorption column group and rectifying column, gas pipeline passes through liquefaction plate to change；It is cold
Freeze unit 8 by refrigerant inlet pipe 81 and refrigerant return line 82 to be connected with condenser, freezes unit refrigerant inlet pipe and refrigerant
Refrigerant siphunculus 83 is additionally provided between return pipe, refrigerant siphunculus passes through liquefaction plate to change；It is additionally provided with compensating plate and changes 11, compensating plate transposition
It is changed between adsorption column group in liquefaction plate, gas conduit passes therethrough, and the evacuated tube of rectifying column also passes therethrough；Condenser
In be additionally provided with refrigerator temperature control galvanic couple 84, freezing unit is equipped with Control of Chiller case 85, refrigerator temperature control galvanic couple and refrigerator
Control cabinet be electrically connected, refrigerator temperature control galvanic couple detection condenser in temperature and feed back to Control of Chiller case to freezing unit into
Row control；It is additionally provided with electric cabinet 12, is electrically connected with heating device, reboiler and the refrigerator group outside adsorption column, and right
Heating device, reboiler and freezing unit outside adsorption column are controlled.
Wherein, copper silver adsorbent of molecular sieve is by there is the raw material of following parts by weight to be made：100 parts of zeolite molecular sieve, 10wt% nitre
Sour 13 parts of solution of silver, 10 parts of 10wt% copper nitrate solutions, 1 part of citric acid, 10 parts of water；
Copper silver adsorbent of molecular sieve is made by following steps：Silver nitrate solution and copper nitrate solution are mixed to prepare mixed solution simultaneously
Mixed solution is heated to 80 DEG C, is added zeolite molecular sieve thereto, while the citric acid obtained citric acid that is dissolved in the water is molten
Citric acid solution is then added slowly in mixed solution by liquid, is stirred, is added with the rotating speed of 60rpm in adding procedure
Continue to stir 3 hours obtained wet gels after adding into, xerogel is made after then wet gel is dried and crushed in 120 DEG C
Powder is finally sintered 2 hours under 550 DEG C but its atmosphere, and copper silver adsorbent of molecular sieve is made after cooling；Zeolite molecular sieve is using
Preceding elder generation calcines 30 minutes under 600 DEG C of high-temperature oxygen environment, and the sodium nitrate that 0.1moml/L is put into after being cooled to room temperature is molten
It impregnates 20 minutes, is dried after being then rinsed with water 3 times for use in liquid.
Embodiment 2
As shown in Figure 1, a kind of carbon dioxide purification device comprising fluid reservoir 1, vaporizer 2, adsorption column group 3, liquefaction plate change 4,
Rectifying column 5, condenser 6, reboiler 7 and freezing unit 8；Fluid reservoir, vaporizer, adsorption column group and rectifying column pass sequentially through gas
Pipeline 9 connects；There are four adsorption columns to form for adsorption column group, respectively is desulfurization removing nitric column 31, dry column 32, de- 33 and of hydrocarbon column
Dealcoholysis full gear column 34, desulfurization removing nitric column are equipped with the adsorbent that is made of aluminium oxide, activated carbon and sodium hydroxide, dry column be equipped with by
The drier of activated carbon and silica gel composition takes off hydrocarbon column and copper silver adsorbent of molecular sieve is housed, and dealcoholysis full gear column is equipped with by zeolite molecules
The adsorbent of sieve and vanadic anhydride composition, four adsorption columns are respectively equipped with independent heating device 35 outside；Condenser is located at essence
It evaporates above tower, the evacuated tube 10 of rectifying column passes through condenser；Reboiler is connected with rectifying column and is located at the lower section of rectifying column, then
It is additionally provided with heater 71 in boiling device；Plate transposition liquefy between adsorption column group and rectifying column, gas pipeline passes through liquefaction plate to change；It is cold
Freeze unit 8 by refrigerant inlet pipe 81 and refrigerant return line 82 to be connected with condenser, freezes unit refrigerant inlet pipe and refrigerant
Refrigerant siphunculus 83 is additionally provided between return pipe, refrigerant siphunculus passes through liquefaction plate to change；It is additionally provided with compensating plate and changes 11, compensating plate transposition
It is changed between adsorption column group in liquefaction plate, gas conduit passes therethrough, and the evacuated tube of rectifying column also passes therethrough；Condenser
In be additionally provided with refrigerator temperature control galvanic couple 84, freezing unit is equipped with Control of Chiller case 85, refrigerator temperature control galvanic couple and refrigerator
Control cabinet be electrically connected, refrigerator temperature control galvanic couple detection condenser in temperature and feed back to Control of Chiller case to freezing unit into
Row control；It is additionally provided with electric cabinet 12, is electrically connected with heating device, reboiler and the refrigerator group outside adsorption column, and right
Heating device, reboiler and freezing unit outside adsorption column are controlled.
Wherein, copper silver adsorbent of molecular sieve is by there is the raw material of following parts by weight to be made：100 parts of zeolite molecular sieve, 10wt% nitre
Sour 15 parts of solution of silver, 12 parts of 10wt% copper nitrate solutions, 2 parts of citric acid, 20 parts of water；
Copper silver adsorbent of molecular sieve is made by following steps：Silver nitrate solution and copper nitrate solution are mixed to prepare mixed solution simultaneously
Mixed solution is heated to 90 DEG C, is added zeolite molecular sieve thereto, while the citric acid obtained citric acid that is dissolved in the water is molten
Citric acid solution is then added slowly in mixed solution by liquid, is stirred, is added with the rotating speed of 90rpm in adding procedure
Continue to stir 4 hours obtained wet gels after adding into, xerogel is made after then wet gel is dried and crushed in 135 DEG C
Powder is finally sintered 4 hours under 570 DEG C but its atmosphere, and copper silver adsorbent of molecular sieve is made after cooling；Zeolite molecular sieve is using
Preceding elder generation calcines 35 minutes under 650 DEG C of high-temperature oxygen environment, and the sodium nitrate that 0.3moml/L is put into after being cooled to room temperature is molten
It impregnates 25 minutes, is dried after being then rinsed with water 3 times for use in liquid.
Embodiment 3
As shown in Figure 1, a kind of carbon dioxide purification device comprising fluid reservoir 1, vaporizer 2, adsorption column group 3, liquefaction plate change 4,
Rectifying column 5, condenser 6, reboiler 7 and freezing unit 8；Fluid reservoir, vaporizer, adsorption column group and rectifying column pass sequentially through gas
Pipeline 9 connects；There are four adsorption columns to form for adsorption column group, respectively is desulfurization removing nitric column 31, dry column 32, de- 33 and of hydrocarbon column
Dealcoholysis full gear column 34, desulfurization removing nitric column are equipped with the adsorbent that is made of aluminium oxide, activated carbon and sodium hydroxide, dry column be equipped with by
The drier of activated carbon and silica gel composition takes off hydrocarbon column and copper silver adsorbent of molecular sieve is housed, and dealcoholysis full gear column is equipped with by zeolite molecules
The adsorbent of sieve and vanadic anhydride composition, four adsorption columns are respectively equipped with independent heating device 35 outside；Condenser is located at essence
It evaporates above tower, the evacuated tube 10 of rectifying column passes through condenser；Reboiler is connected with rectifying column and is located at the lower section of rectifying column, then
It is additionally provided with heater 71 in boiling device；Plate transposition liquefy between adsorption column group and rectifying column, gas pipeline passes through liquefaction plate to change；It is cold
Freeze unit 8 by refrigerant inlet pipe 81 and refrigerant return line 82 to be connected with condenser, freezes unit refrigerant inlet pipe and refrigerant
Refrigerant siphunculus 83 is additionally provided between return pipe, refrigerant siphunculus passes through liquefaction plate to change；It is additionally provided with compensating plate and changes 11, compensating plate transposition
It is changed between adsorption column group in liquefaction plate, gas conduit passes therethrough, and the evacuated tube of rectifying column also passes therethrough；Condenser
In be additionally provided with refrigerator temperature control galvanic couple 84, freezing unit is equipped with Control of Chiller case 85, refrigerator temperature control galvanic couple and refrigerator
Control cabinet be electrically connected, refrigerator temperature control galvanic couple detection condenser in temperature and feed back to Control of Chiller case to freezing unit into
Row control；It is additionally provided with electric cabinet 12, is electrically connected with heating device, reboiler and the refrigerator group outside adsorption column, and right
Heating device, reboiler and freezing unit outside adsorption column are controlled.
Wherein, copper silver adsorbent of molecular sieve is by there is the raw material of following parts by weight to be made：100 parts of zeolite molecular sieve, 10wt% nitre
Sour 18 parts of solution of silver, 15 parts of 10wt% copper nitrate solutions, 3 parts of citric acid, 30 parts of water；
Copper silver adsorbent of molecular sieve is made by following steps：Silver nitrate solution and copper nitrate solution are mixed to prepare mixed solution simultaneously
Mixed solution is heated to 100 DEG C, is added zeolite molecular sieve thereto, while the citric acid obtained citric acid that is dissolved in the water is molten
Citric acid solution is then added slowly in mixed solution by liquid, is stirred, is added with the rotating speed of 120rpm in adding procedure
Continue to stir 5 hours obtained wet gels after adding into, xerogel is made after then wet gel is dried and crushed in 150 DEG C
Powder is finally sintered 6 hours under 600 DEG C but its atmosphere, and copper silver adsorbent of molecular sieve is made after cooling；Zeolite molecular sieve is using
Preceding elder generation calcines 40 minutes under 700 DEG C of high-temperature oxygen environment, and the sodium nitrate that 0.5moml/L is put into after being cooled to room temperature is molten
It impregnates 30 minutes, is dried after being then rinsed with water 4 times for use in liquid.
In above-described embodiment, it is all made of raw material commonly used in the art unless otherwise specified；Above-described embodiment adsorption column simultaneously
The dosage of adsorbent is selected accordingly according to the amount and processing speed of the carbon dioxide of required processing in each adsorption column in group.
It is pure that the purity of carbon dioxide through above-described embodiment after purification can reach 99.999% or even 99.9995% or more
Degree, can meet national standard GB/T 23938-2009, and yield can also reach 50kg/h.
It should be understood that those skilled in the art, can be improved or be become according to the above description
It changes, and all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (10)
1. a kind of carbon dioxide purification device, it is characterised in that：It include fluid reservoir, vaporizer, adsorption column group, liquefaction plate change,
Rectifying column, condenser, reboiler and freezing unit；Fluid reservoir, vaporizer, adsorption column group and rectifying column pass sequentially through gas pipeline
Connection, condenser are located above rectifying column, and the evacuated tube of rectifying column passes through condenser, reboiler to be connected and be located at rectifying column
The lower section of rectifying column is additionally provided with heater in reboiler；Plate transposition liquefy between adsorption column group and rectifying column, gas pipeline is worn
Liquefaction plate is crossed to change；Freezing unit is connected by refrigerant inlet pipe and refrigerant return line with condenser, and unit refrigerant inlet pipe is freezed
Refrigerant siphunculus is additionally provided between refrigerant return line, refrigerant siphunculus passes through liquefaction plate to change.
2. a kind of carbon dioxide purification device according to claim 1, it is characterised in that：It is additionally provided with compensating plate and changes, and mends
It repays plate transposition to change between adsorption column group in liquefaction plate, gas conduit passes therethrough, and the evacuated tube of rectifying column is also from wherein wearing
It crosses.
3. a kind of carbon dioxide purification device according to claim 1, it is characterised in that：It is additionally provided in the condenser
Refrigerator temperature control galvanic couple, freezing unit are equipped with Control of Chiller case, refrigerator temperature control galvanic couple and the electrical connection of Control of Chiller case.
4. a kind of carbon dioxide purification device according to claim 1, it is characterised in that：There are four the adsorption column groups
Adsorption column forms, respectively desulfurization removing nitric column, dry column, de- hydrocarbon column and dealcoholysis full gear column.
5. a kind of carbon dioxide purification device according to claim 4, it is characterised in that：Divide outside four adsorption columns
It She You not independent heating device.
6. a kind of carbon dioxide purification device according to claim 1 or 5, it is characterised in that：It is additionally provided with electric cabinet,
It is electrically connected with heating device, reboiler and the refrigerator group outside adsorption column.
7. a kind of carbon dioxide purification device according to claim 4, it is characterised in that：The desulfurization removing nitric column is equipped with
The adsorbent being made of aluminium oxide, activated carbon and sodium hydroxide, the drying column is equipped with to be done by what activated carbon and silica gel formed
Drying prescription, the de- hydrocarbon column are equipped with copper silver adsorbent of molecular sieve, and the dealcoholysis full gear column is equipped with by zeolite molecular sieve and five oxygen
Change the adsorbent of two vanadium composition.
8. a kind of carbon dioxide purification device according to claim 7, it is characterised in that the copper silver molecular sieve absorption
Agent is by there is the raw material of following parts by weight to be made：100 parts of zeolite molecular sieve, 13~18 parts of 10wt% silver nitrate solutions, 10wt% nitric acid
10~15 parts of copper solution, 1~3 part of citric acid, 10~30 parts of water.
9. a kind of carbon dioxide purification device according to claim 8, it is characterised in that the copper silver molecular sieve absorption
Agent is made by following steps：Silver nitrate solution and copper nitrate solution are mixed to prepare mixed solution and mixed solution is heated to 80
~100 DEG C, while citric acid being dissolved in the water obtained citric acid solution, then citric acid solution is added slowly to mix
It in solution, is stirred with the rotating speed of 60~120rpm in adding procedure, zeolite molecular sieve is added after the completion of addition thereto and connects
It and continues 3~5 hours obtained wet gels of stirring, xerogel is made after then wet gel is dried and crushed in 120~150 DEG C
Powder is finally sintered 2~6 hours under 550~600 DEG C but its atmosphere, and copper silver adsorbent of molecular sieve is made after cooling.
10. a kind of carbon dioxide purification device according to claim 8 or claim 9, it is characterised in that：
The zeolite molecular sieve is calcined 30~40 minutes using preceding elder generation under 600~700 DEG C of high-temperature oxygen environment, is cooled to
It is put into the sodium nitrate solution of 0.1~0.5moml/L and is impregnated 20~30 minutes after room temperature, is then rinsed with water 3~4 times
Drying is for use afterwards.
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