CN103936543A - Method for synchronously obtaining carbon dioxide absorbent along with production of acetylene - Google Patents
Method for synchronously obtaining carbon dioxide absorbent along with production of acetylene Download PDFInfo
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- CN103936543A CN103936543A CN201410137926.5A CN201410137926A CN103936543A CN 103936543 A CN103936543 A CN 103936543A CN 201410137926 A CN201410137926 A CN 201410137926A CN 103936543 A CN103936543 A CN 103936543A
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- carbide
- acetylene
- carbon dioxide
- carbon
- dioxide absorbent
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 275
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 112
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 69
- 230000002745 absorbent Effects 0.000 title claims abstract description 47
- 239000002250 absorbent Substances 0.000 title claims abstract description 47
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 61
- 238000001354 calcination Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000005997 Calcium carbide Substances 0.000 claims description 36
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 36
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 16
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 16
- WBXQXRXMGCOVHA-UHFFFAOYSA-N [methyl(nitroso)amino]methyl acetate Chemical compound O=NN(C)COC(C)=O WBXQXRXMGCOVHA-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 82
- 230000008569 process Effects 0.000 abstract description 22
- 230000007613 environmental effect Effects 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 abstract 2
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229960004424 carbon dioxide Drugs 0.000 description 110
- 235000011089 carbon dioxide Nutrition 0.000 description 53
- 239000003795 chemical substances by application Substances 0.000 description 45
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 36
- 239000000292 calcium oxide Substances 0.000 description 34
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 33
- 235000012255 calcium oxide Nutrition 0.000 description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000005431 greenhouse gas Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000003245 coal Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- -1 Wingdale Chemical class 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for synchronously obtaining a carbon dioxide absorbent along with production of acetylene and belongs to the technical fields of recycling of industrial base solid wastes and low-carbon environmental protection. The method disclosed by the invention comprises the following steps: simultaneously adding aluminum oxide (Al2O3) or aluminum hydroxide (Al(OH)3) or aluminum nitrate nonahydrate (Al(NO3)3.9H2O), carbide and water into an acetylene generator for full reaction, dehydrating an obtained carbide slag slurry mixture, and then calcining to obtain the carbon dioxide absorbent. The method disclosed by the invention fully utilizes the process characteristics of production of the acetylene by a carbide hydrolysis method; by adding an appropriate amount of aluminum oxide or aluminum hydroxide or aluminum nitrate nonahydrate material, and performing simple drying and calcination process, the carbon dioxide absorbent with high absorption capacity and good cyclic stability can be obtained, and the method has important significance in the field of low-carbon environmental protection; and the invention further provides a novel treatment and disposal method of base solid waste carbide slag produced by production of the acetylene by hydrolysis of the carbide.
Description
Technical field
The present invention relates to a kind of method of following acetylene synchronization gain carbon-dioxide absorbent, belong to solid waste cycling and reutilization and low-carbon environment-friendly field.
Background technology
Carbonic acid gas is as most important artificial greenhouse gases, and its total emission volumn has increased approximately 80% during 1970 to 2004.Atmospheric carbon dioxide levels rises and causes global warming, thereby physical environment and human society have been produced to series of negative impact, and therefore carbonic acid gas problem is subject to the extensive concern of international community.According to (the Intergovernmental Panel on Climate Change of Intergovernmental Panel on Climate Change, IPCC) demonstration of giving information: global stationary source (carbonic acid gas year discharge scale >=0.1 Mt) the average annual total emission volumn of carbonic acid gas is 13.47 Gt, and wherein the CO2 emissions of coal-burning power plant accounts for total emission volumn 40%.China's energy consumption structure is taking coal as main (within 2009, coal in China accounts for 70% in primary energy source consumption structure, expects the year two thousand thirty this ratio and will be elevated to 70.32%), and CO2 emissions is only second to the U.S. at present, and row occupy the whole world second.On the one hand, follow the quickening of process of industrialization and the dependence to fossil energies such as coals, China's greenhouse gas emissions will continue to increase in a short time.Expect the year two thousand thirty, China's CO2 emissions will exceed the U.S.; On the other hand, China faces again huge carbon dioxide discharge-reduction pressure.The Chinese government is the formal action target of externally announcing to control greenhouse gas emission in 2009 11 years 26 days, determines that the gross domestic product Carbon emission of the year two thousand twenty unit was than decline 40%-45% in 2005.Therefore, actively develop the research of carbonic acid gas control techniques in China and both contributed to alleviate the climate change problem causing because of carbonic acid gas, contribute to again to promote the contractual capacity of China's carbon dioxide discharge-reduction simultaneously.Carbonic acid gas measure of control mainly comprise: (1) improves energy conversion rate and utilization ratio.(2) promote the use of the low-carbon energies such as nuclear energy, wind energy and hydraulic energy.(3) utilize the ecosystems such as forest, soil and ocean to strengthen naturally converging of carbonic acid gas.(4) implement collecting carbonic anhydride and Plugging Technology Applied (Carbon dioxide Capture & Sequestration, CCS).Compare other three kinds of measure of control, collecting carbonic anhydride and Plugging Technology Applied can fast and effeciently be controlled atmosphere percent of greenhouse gases concentration, and this technology has the potentiality that reduce reduction of greenhouse gas discharge cost and improve reduction of greenhouse gas discharge handiness.It is reported, collecting carbonic anhydride and Plugging Technology Applied can be cut down 20% carbonic acid gas of energy industry discharge in following global range.2005, the achievement in research about collecting carbonic anhydride and Plugging Technology Applied in world wide has been enumerated in " special event of CCS technology " thematic activity of Intergovernmental Panel on Climate Change's tissue, and think that collecting carbonic anhydride and Plugging Technology Applied are " welcome " technology of defence Global warming, finally this technology is above adopted in the 12nd Conference of the Parties (COP12).
Collecting carbonic anhydride and Plugging Technology Applied be first by collecting carbonic anhydride technology, by the carbon dioxide separation of industry and the discharge of relevant energy industry out, then by carbonic acid gas Plugging Technology Applied by its conveying and seal seabed up for safekeeping or specific geologic trap.Therefore the collecting carbonic anhydride technology that, research and development have obvious economic benefit and an environmental benefit is the prerequisite of successful implementation collecting carbonic anhydride and Plugging Technology Applied.Collecting carbonic anhydride method mainly comprises absorption process, absorption method, membrane separation process and separation by deep refrigeration.Wherein, Chinese scholars is to having carried out deep research work taking calcination/carbonation reaction principle as basic collecting carbonic anhydride technology.As shown in Figure 1, this utilization calcium oxide (CaO) base absorbant participates in carbonation reaction (CaO+CO
2=CaCO
3) carbonic acid gas of trapping in flue gas, then under specified temp to reaction product calcium carbonate (CaCO
3) carry out calcining and decomposing (CaCO
3=CaO+CO
2), thereby the carbon dioxide that obtains high density is for follow-up sealing up for safekeeping or recycling, realizes the regeneration of calcium oxide-based absorption agent simultaneously and enters the next carbonation reaction cycle.The calcium oxide-based absorption agent of research report mainly comprises that (main component is CaCO to Wingdale at present
3), (main component is CaCO to calcite
3) and rhombspar (main component is CaCO
3mgCO
3).The natural crystal such as Wingdale and rhombspar belongs to Nonrenewable resources, and overexploitation will cause the havoc of the ecotopes such as geology, the hydrology and earth's surface resource.Simultaneously, because the regeneration of calcium oxide-based absorption agent depends on hot environment, research has confirmed the hole development degree of high temperature sintering phenomenon meeting impair absorption agent, therefore will cause carbon dioxide absorption efficiency constantly decay along with increasing of cycle index of calcium oxide-based absorption agent.Bibliographical information: utilize natural limestone after 1000 circularly trapping carbon dioxide reactions, its remaining transformation efficiency is only 3.5%.Thereby above-mentioned shortcoming has greatly limited the application prospect of the natural calcium oxide-based ores such as Wingdale aspect carbon dioxide removal.In addition, thereby the decomposition reaction that utilizes the natural calcium oxide-based ores such as Wingdale that calcium carbonate can occur in calcination process first additionally produces a certain amount of carbon dioxide (taking calcium carbonate content as 90% calculating, calcine 1 t Wingdale and will produce 0.396 t carbonic acid gas), thus the environmental benefit of the natural calcium oxide-based absorption agent capturing carbon dioxides such as Wingdale weakened to a certain extent.
In order to make up the deficiency of natural calcium oxide-based absorption agent, must seek the substitute that a kind of environmental friendliness and reactive behavior are better than the natural absorption agents such as natural limestone.Known by the commercial run that investigation is relevant to calcium oxide material, (main component is calcium hydroxide (Ca (OH) to the carbide slag discharging in calcium carbide hydrolysis legal system acetylene technological process
2)), (main component is calcium carbonate (CaCO for the white clay that discharges in papermaking process
3)) all can be used as the calcium oxide-based absorption agent source of capturing carbon dioxide.Wherein, the main ingredient of the carbide slag of acetylene industry discharge is calcium hydroxide, document has confirmed that the activity of calcium hydroxide circulation absorbing carbon dioxide is obviously better than calcium carbonate, therefore there are the potentiality of capturing carbon dioxide without the carbide slag sample of any processing itself, but in order to obtain as basis the carbon-dioxide absorbent that has more excellent cycle reactive behavior taking carbide slag material, must take certain measure to modify carbide slag, thereby further improve the cyclical stability of its absorbing carbon dioxide.
Carbide slag is the solid by-product taking calcium carbide as raw material production acetylene, and main ingredient is calcium hydroxide, with oxide compound or the oxyhydroxide of silicon, iron, aluminium, magnesium, sulphur, phosphorus.It is reported, China's carbide slag ultimate production reaches 1,800 ten thousand tons/year, accounts for the 1:3 of global carbide slag turnout.Processing and the disposal options of carbide slag mainly comprise at present: (1) is filled out sea, filled out the regular stacking of ditch; (2) after natural subsidence, sell; (3) calcium carbide waste slag replaces lime cement made of stones; (4) produce unslaked lime as carbide raw material; (5) produce light cinder brick; (6) calcium carbide waste slag is as industrial chemicals.Processing and the disposal options of at present carbide slag is filled out to sea, filling out the regular stacking of ditch will be occupied a large amount of soils, pollute shallow ground water and cause salting of soil, above-mentioned measure can not be carried out this trade waste of carbide slag effectively utilizing and administering, and therefore recycling is the most scientific and reasonable processing of carbide slag and disposal options.So far, carbide slag recycling approach has: the Chinese invention patent that the patent No. is ZL200710148467.0 has been introduced a kind of method of utilizing carbide slag slurries to produce high-performance solid desulfurizing agent; The patent No. is that the Chinese invention patent of ZL200610124541.0 has been introduced a kind of method of utilizing industrial waste carbide slag to produce calcium chloride; The patent No. is that the Chinese invention patent of ZL201010615521.X has been introduced a kind of method of producing nitrocalcite with carbide slag.
Along with large scale mining and the application of the fossil energies such as coal, oil, Sweet natural gas, the global warming issue that main artificial greenhouse gases carbonic acid gas causes is increasingly severe, and therefore international community has carried out deep cooperation and the broad research of policy, regulation and technological layer in reduction of greenhouse gas discharge field.For technician, the carbon dioxide discharge-reduction technology that research and development have obvious economic benefit and environmental benefit is core missions.There is the problem that environmental benefit is low, absorption agent reduction coefficient large and carbide slag brings pollution as trade waste to environment and can not effectively utilize in the comprehensive above-mentioned natural calcium oxide-based absorption agent circulation absorbing carbon dioxide methods such as Wingdale of utilizing, the present invention is with the comprehensive regulation, raising environmental benefit is starting point, has proposed a kind of method of following acetylene synchronization gain carbon-dioxide absorbent.
Summary of the invention
The object of the invention is to the deficiency in order to make up carbide slag absorbing carbon dioxide, a kind of method of following acetylene synchronization gain carbon-dioxide absorbent is provided, the carbon-dioxide absorbent that the method on the one hand can be convenient, obtain good reactive behavior efficiently, a kind of novel method of carbide slag high-efficiency resource recycling is provided on the other hand, has realized the target of trade waste cycling and reutilization.
The method of following acetylene synchronization gain carbon-dioxide absorbent of the present invention, specifically comprises the following steps:
(1) one in aluminum oxide, aluminium hydroxide, ANN aluminium nitrate nonahydrate and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of aluminum oxide and calcium carbide is 7:100-15:100, the mass ratio of aluminium hydroxide and calcium carbide is 10:100-20:100, the mass ratio of ANN aluminium nitrate nonahydrate and calcium carbide is 50:100-100:100, the mass ratio of water and calcium carbide is 350:100-1000:100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 100-110 DEG C, freeze-day with constant temperature 12-24 h obtains solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1-2 h calcining at 850-900 DEG C, obtains carbon-dioxide absorbent.
The present invention utilizes X-ray diffraction (XRD) to characterize and finds that the process of calcining the drying carbide slag material that contains aluminum oxide or aluminium hydroxide or ANN aluminium nitrate nonahydrate has generated C 12 A 7 (Ca
12al
14o
33).
Reaction principle of the present invention is:
While adding aluminum oxide: Ca (OH)
2=CaO+H
2o
Wherein partial CaO and aluminum oxide react: 12CaO+7Al
2o
3=Ca
12al
14o
33
While adding aluminium hydroxide: Ca (OH)
2=CaO+H
2o
Wherein partial CaO and aluminium hydroxide react: 12CaO+14Al (OH)
3=Ca
12al
14o
33+ 21H
2o
While adding ANN aluminium nitrate nonahydrate: Ca (OH)
2=CaO+H
2o
Wherein partial CaO and ANN aluminium nitrate nonahydrate react:
24CaO+28Al(NO
3)
3·9H
2O=2Ca
12Al
14O
33+21O
2+84NO
2+252H
2O
Therefore consist of the mixture of calcium oxide and C 12 A 7 by the material of step (3) acquisition carbon-dioxide absorbent.
A kind of method of following acetylene synchronization gain carbon-dioxide absorbent proposing according to the present invention, in described step (1), the amount of the aluminum oxide adding in carbide-feed generator or aluminium hydroxide or ANN aluminium nitrate nonahydrate can ensure in carbon-dioxide absorbent that step (3) obtains in calcium oxide and the optimum range of C 12 A 7 mass ratio in 65:35-85:15.
The method of following acetylene synchronization gain carbon-dioxide absorbent that the present invention proposes, because carbide slag main component is calcium hydroxide, thereby in calcination process, what mainly occur is calcium hydroxide decomposition reaction, compare and utilize Wingdale, the calcining first of the raw material such as calcite or rhombspar, the process of calcining the solid-state carbide slag of salic or aluminium hydroxide or ANN aluminium nitrate nonahydrate can release of carbon dioxide, for the carbon-dioxide absorbent obtaining, carbon dioxide absorption performance measurement is found, C 12 A 7 is as inert component, himself do not participate in the reaction of absorbing carbon dioxide, but it can effectively suppress or alleviate the intercrystalline sintering of calcium oxide as dispersion medium, therefore improved largely the cyclical stability of the novel oxidation calcium-based ascarite obtaining by the present invention.
The present invention utilizes calcium carbide hydrolysis method to produce the operational characteristic of acetylene, by adding appropriate aluminum oxide or aluminium hydroxide or ANN aluminium nitrate nonahydrate and can obtaining efficient carbon-dioxide absorbent through dehydration and the easy steps such as calcining, thereby effectively make up and utilize at present in the natural calcium oxide-based absorption agent circularly trapping carbonic acid gas processes such as Wingdale assimilated efficiency decay not enough faster.Meanwhile, utilize technique that the present invention proposes to prepare carbon-dioxide absorbent and avoided exploiting the ecological damage problem that natural calcium oxide-based ore causes, and the additional carbon dioxide problem of having avoided the absorption agents such as Wingdale to produce in calcination process.The present invention utilizes industrial solid castoff to administer carbonated flue gas, follows the theory of the treatment of wastes with processes of wastes against one another, embodies distinct environmental benefit and economic benefit, thereby has broad application prospects.
The present invention utilizes respectively micro thermal balance, fixed bed and three kinds of reactors of fluidized-bed to implement the investigation of the carbon dioxide absorption performance of following acetylene synchronization gain effective carbon-dioxide absorption agent of the present invention's proposition.
Beneficial effect of the present invention is:
(1) method of following acetylene synchronization gain carbon-dioxide absorbent of the present invention, it utilizes industrial solid castoff to prepare effective carbon-dioxide absorption agent, has reduced the discharge of carbon dioxide in flue gas;
(2) the invention provides the recycling approach for industrial solid castoff carbide slag, can effectively make up the deficiency of utilizing the natural crystal capturing carbon dioxides such as Wingdale, the present invention is no matter still all have important practical significance for the recycling of carbide slag for the effective elimination of carbon dioxide in flue gas;
(3) carbon-dioxide absorbent that prepared by the present invention is the mixture of calcium oxide and C 12 A 7, calcining: in the process of carbonating circularly trapping carbonic acid gas, C 12 A 7 be not with the inert substance of carbon dioxide reaction, it is scattered in calcium oxide intergranule as medium, therefore, than the conventional carbon-dioxide absorbent such as Wingdale, rhombspar, C 12 A 7 is the sintering of inhibited oxidation calcium in circularly trapping carbonic acid gas process effectively, improves the carbonic acid gas circulation assimilating activity of absorption agent;
(4) aluminum oxide or aluminium hydroxide or ANN aluminium nitrate nonahydrate can be improved the dispersing property of solid materials, therefore in calcium carbide hydrolysis acetylene processed, add aluminum oxide or aluminium hydroxide or ANN aluminium nitrate nonahydrate can improve the dispersiveness of calcium carbide particle, thereby strengthen the solid-liquid contact area between calcium carbide and water, be conducive to improve generating rate and the output of acetylene.
Brief description of the drawings
Fig. 1 is calcium oxide-based absorption agent circularly trapping carbonic acid gas schematic diagram;
Fig. 2 is process flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details, but protection scope of the present invention is not limited to described content.
Embodiment 1
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps, as shown in Figure 2:
(1) aluminum oxide and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of aluminum oxide and calcium carbide is 7:100, and the mass ratio of water and calcium carbide is 350:100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 100 DEG C, freeze-day with constant temperature 24 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 2 h calcinings at 850 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 7.35%.
As shown in Figure 1, utilize micro thermal balance reactor to contrast according to the carbon-dioxide absorbent of the present invention's acquisition and the carbonic acid gas circulation absorptive character of commercially available analytical pure calcium hydroxide.The absorbent preparation that the present invention prepares is particle diameter 60-80 order, calcination reaction temperature 840-900 DEG C, and calcination time 10-20 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; Carbonation reaction temperature 650-700 DEG C, carbonating times 20 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen, altogether examines or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 60 circularly trapping carbonic acid gas.
Result shows: (1) the 60th calcining: carbonating circulation end, and the absorption agent that the present invention obtains and the carbon dioxide absorption efficiency of commercially available analytical pure calcium hydroxide are respectively 62.53% and 23.18%; (2) in 60 circulation absorbing carbon dioxide processes, there is not obvious decay in the carbon dioxide absorption efficiency of the absorption agent that the present invention obtains, but the carbon dioxide absorption efficiency of commercially available analytical pure calcium hydroxide but by the 1st time 63.13% decay to the 60th time 23.18%, attenuation amplitude is 63.28%.
Thereby show: taking micro thermal balance reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available analytical pure calcium hydroxide, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Embodiment 2
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps:
(1) aluminum oxide and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of aluminum oxide and calcium carbide is 15:100, and the mass ratio of water and calcium carbide is 1000:100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 110 DEG C, freeze-day with constant temperature 12 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1 h calcining at 900 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 6.28%.
Utilize micro thermal balance reactor to contrast according to the carbon-dioxide absorbent of the present invention's acquisition and the carbonic acid gas circulation absorptive character of commercially available analytical pure calcium carbonate.Absorption agent particle diameter: 60-80 order, calcination reaction temperature 840-900 DEG C, calcination time 10-20 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; Carbonation reaction temperature 650-700 DEG C, carbonating times 20 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen.Altogether examine or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 60 circularly trapping carbonic acid gas.
Result shows: (1) the 60th calcining: carbonating circulation end, and the absorption agent that the present invention obtains and the carbon dioxide absorption efficiency of commercially available analytical pure calcium carbonate are respectively 62.53% and 16.18%; (2) in 60 circulation absorbing carbon dioxide processes, there is not obvious decay in the carbon dioxide absorption efficiency of the absorption agent that the present invention obtains, but the carbon dioxide absorption efficiency of commercially available analytical pure calcium carbonate but by the 1st time 68.27% decay to the 60th time 16.18%, attenuation amplitude is 76.30%.
Thereby show: taking micro thermal balance reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available analytical pure calcium carbonate, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Embodiment 3
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps:
(1) aluminium hydroxide and calcium carbide, water are joined in reactor simultaneously, wherein the mass ratio of aluminium hydroxide and calcium carbide is 20:100, and the mass ratio of water and calcium carbide is 350: 100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 102 DEG C, freeze-day with constant temperature 14 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1.2 h calcinings at 860 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 6.57%.
Utilize fixed-bed reactor to contrast the absorption agent of the present invention's acquisition and the carbonic acid gas circulation absorptive character of commercially available Wingdale.Absorption agent particle diameter: 60-80 order, calcination reaction temperature 900-940 DEG C, calcination time 5-10 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; 700 DEG C of carbonation reaction temperature, carbonating times 20 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen.Altogether examine or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 40 circularly trapping carbonic acid gas.
Result shows: (1) 40 circulation end, and the carbon dioxide absorption efficiency of gained absorption agent of the present invention and commercially available Wingdale is respectively 58.93% and 22.37%; In (2) 40 circularly trapping processes, there is not obvious decay in gained absorption agent of the present invention, however the carbon dioxide absorption efficiency of commercially available Wingdale but by the 1st time 69.52% decay to the 40th time 22.37%, attenuation amplitude is 67.82%.
Thereby show: taking fixed-bed reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available Wingdale, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Embodiment 4
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps:
(1) aluminium hydroxide and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of aluminium hydroxide and calcium carbide is 10:100, and the mass ratio of water and calcium carbide is 1000: 100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 104 DEG C, freeze-day with constant temperature 16 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1.4 h calcinings at 880 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 5.73%.
Utilize fluidized-bed reactor to contrast the absorption agent of the present invention's acquisition and carbonic acid gas-circulation absorptive character of commercially available Wingdale.Absorption agent particle diameter: 120-140 order, 900 DEG C of calcination reaction temperature, calcination time 5 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; 700 DEG C of carbonation reaction temperature, carbonating times 10 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen.Altogether examine or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 60 circularly trapping carbonic acid gas.
Result shows: (1) 60 circulation end, and the carbon dioxide absorption efficiency of gained absorption agent of the present invention and commercially available Wingdale is respectively 56.47% and 18.28%; In (2) 60 circularly trapping processes, there is not obvious decay in gained absorption agent of the present invention, however the carbon dioxide absorption efficiency of commercially available Wingdale but by the 1st time 60.83% decay to the 60th time 18.28%, attenuation amplitude is 69.95%.
Thereby show: taking fluidized-bed reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available Wingdale, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Embodiment 5
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps:
(1) ANN aluminium nitrate nonahydrate and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of ANN aluminium nitrate nonahydrate and calcium carbide is 50:100, and the mass ratio of water and calcium carbide is 350: 100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 108 DEG C, freeze-day with constant temperature 18 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1.8 h calcinings at 900 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 6.18%.
Utilize fluidized-bed reactor to contrast the absorption agent of the present invention's acquisition and carbonic acid gas-circulation absorptive character of commercially available Wingdale.Absorption agent particle diameter: 120-140 order, 900 DEG C of calcination reaction temperature, calcination time 5 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; 700 DEG C of carbonation reaction temperature, carbonating times 10 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen.Altogether examine or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 60 circularly trapping carbonic acid gas.
Result shows: (1) 60 circulation end, and the carbon dioxide absorption efficiency of gained absorption agent of the present invention and commercially available Wingdale is respectively 55.28% and 18.28%; In (2) 60 circularly trapping processes, there is not obvious decay in gained absorption agent of the present invention, however the carbon dioxide absorption efficiency of commercially available Wingdale but by the 1st time 60.83% decay to the 60th time 18.28%, attenuation amplitude is 69.95%.
Thereby show: taking fluidized-bed reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available Wingdale, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Embodiment 6
The method of following acetylene synchronization gain carbon-dioxide absorbent described in the present embodiment, specifically comprises the following steps:
(1) ANN aluminium nitrate nonahydrate and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of ANN aluminium nitrate nonahydrate and calcium carbide is 1:1, and the mass ratio of water and calcium carbide is 1000: 100, fully after reaction, obtains carbide slag slurries mixture;
(2) carbide slag slurries mixture step (1) being obtained dewaters, and then at 108 DEG C, freeze-day with constant temperature 18 h obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace calcining at constant temperature 1.8 h calcinings at 900 DEG C, obtains carbon-dioxide absorbent.
Compare with existing electricity consumption standby acetylene method made of stones, the acetylene yield that the method for the invention prepares has improved 5.28%.
Utilize fluidized-bed reactor to contrast the absorption agent of the present invention's acquisition and carbonic acid gas-circulation absorptive character of commercially available Wingdale.Absorption agent particle diameter: 120-140 order, 900 DEG C of calcination reaction temperature, calcination time 5 min, calcination atmosphere is the carbonic acid gas of volume fraction 99.95%; 700 DEG C of carbonation reaction temperature, carbonating times 10 min, carbonating atmosphere is the simulated flue gas that the carbonic acid gas of volume fraction 15% is equipped with 85% nitrogen.Altogether examine or check the assimilated efficiency (note: utilize the CaO conversion in absorption agent to characterize carbon dioxide absorption efficiency) of 60 circularly trapping carbonic acid gas.
Result shows: (1) 60 circulation end, and the carbon dioxide absorption efficiency of gained absorption agent of the present invention and commercially available Wingdale is respectively 54.93% and 18.28%; In (2) 60 circularly trapping processes, there is not obvious decay in gained absorption agent of the present invention, however the carbon dioxide absorption efficiency of commercially available Wingdale but by the 1st time 60.83% decay to the 60th time 18.28%, attenuation amplitude is 69.95%.
Thereby show: taking fluidized-bed reactor as carbon dioxide absorption Testing Platform, the carbon-dioxide absorbent that the present invention obtains is compared commercially available Wingdale, has both had good carbon dioxide absorption efficiency, possesses again good circulating reaction activity.
Claims (3)
1. follow a method for acetylene synchronization gain carbon-dioxide absorbent, it is characterized in that specifically comprising the steps:
(1) one in aluminum oxide, aluminium hydroxide, ANN aluminium nitrate nonahydrate and calcium carbide, water are joined in reactor simultaneously, wherein, the mass ratio of aluminum oxide and calcium carbide is 7:100-15:100, the mass ratio of aluminium hydroxide and calcium carbide is 10:100-20:100, the mass ratio of ANN aluminium nitrate nonahydrate and calcium carbide is 50:100-100:100, the mass ratio of water and calcium carbide is 350:100-1000:100, fully after reaction, obtains carbide slag slurries mixture;
(2) after carbide slag slurries mixture step (1) being obtained dewaters, be dried and obtain solid-state carbide slag;
(3) solid-state carbide slag step (2) being obtained is placed in retort furnace and calcines, and obtains carbon-dioxide absorbent.
2. the method for following acetylene synchronization gain carbon-dioxide absorbent according to claim 1, is characterized in that: the drying conditions after the described carbide slag slurries mixture dehydration of step (3) is: freeze-day with constant temperature 12-24 h at 100-110 DEG C.
3. the method for following acetylene synchronization gain carbon-dioxide absorbent according to claim 1, is characterized in that: the calcination condition of the described calcining of step (4) is: calcining at constant temperature 1-2 h at 850-900 DEG C.
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| CN107744716A (en) * | 2017-11-15 | 2018-03-02 | 山东大学 | The hollow compound CO of shell-type carbide slag2Absorbent and its synthetic method and application |
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| CN114522522A (en) * | 2022-01-29 | 2022-05-24 | 武汉理工大学 | Has CO2Calcium-aluminum-based solid waste carrier material with efficient circulating and trapping functions and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107744716B (en) * | 2017-11-15 | 2019-09-06 | 山东大学 | The hollow compound CO of shell-type carbide slag2Absorbent and its synthetic method and application |
| CN114130350A (en) * | 2021-12-20 | 2022-03-04 | 中国科学院过程工程研究所 | CO based on multi-source solid waste modification2Adsorbent and preparation method and application thereof |
| CN114522522A (en) * | 2022-01-29 | 2022-05-24 | 武汉理工大学 | Has CO2Calcium-aluminum-based solid waste carrier material with efficient circulating and trapping functions and preparation method thereof |
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