CN115400579A - Dechlorinating agent and preparation method and application thereof - Google Patents
Dechlorinating agent and preparation method and application thereof Download PDFInfo
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- CN115400579A CN115400579A CN202211154087.9A CN202211154087A CN115400579A CN 115400579 A CN115400579 A CN 115400579A CN 202211154087 A CN202211154087 A CN 202211154087A CN 115400579 A CN115400579 A CN 115400579A
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- dechlorinating
- calcium carbonate
- composite reinforcing
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- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 97
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 7
- 238000006298 dechlorination reaction Methods 0.000 claims description 22
- 241000219782 Sesbania Species 0.000 claims description 18
- 229920000609 methyl cellulose Polymers 0.000 claims description 16
- 239000001923 methylcellulose Substances 0.000 claims description 16
- 235000010981 methylcellulose Nutrition 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 239000004113 Sepiolite Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052624 sepiolite Inorganic materials 0.000 claims description 5
- 235000019355 sepiolite Nutrition 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000001833 catalytic reforming Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000460 chlorine Substances 0.000 abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 abstract description 16
- 238000002407 reforming Methods 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 5
- 230000001172 regenerating effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 239000007789 gas Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 239000003463 adsorbent Substances 0.000 description 5
- 239000000440 bentonite Substances 0.000 description 5
- 229910000278 bentonite Inorganic materials 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003819 basic metal compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
- B01D53/685—Halogens or halogen compounds by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
- B01D2257/2045—Hydrochloric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention relates to a dechlorinating agent and a preparation method and application thereof, wherein the dechlorinating agent comprises an active compound, a carrier forming agent and a composite reinforcing agent; the active compound comprises an alkaline earth metal compound; the carrier forming agent comprises alumina, a molecular sieve and minerals; the composite reinforcing agent comprises calcium carbonate and sodium hydroxide. The dechlorinating agent has the advantages of high chlorine capacity, high mechanical strength, long service life, cracking resistance and the like, and meets the working condition of continuously reforming and regenerating flue gas.
Description
Technical Field
The invention relates to the technical field of dechlorinating agents, and particularly relates to a dechlorinating agent and a preparation method and application thereof.
Background
In the petroleum refining industry, with the continuous development of catalytic reforming technology and the continuous improvement of the processing capacity of a reforming device, the hydrogen chloride generated in the section is increased gradually, and a large amount of organic chloride is reacted to generate hydrogen chloride which is combined with water in a system to generate strong corrosive hydrochloric acid to corrode equipment, thereby causing serious influence on normal production. Therefore, removal of hydrogen chloride is essential. At present, the dechlorinating agent for removing chlorine-containing gas in a reforming device still has the defects of unsatisfactory dechlorinating effect and insufficient crushing strength in use, the chlorine capacity of the high-temperature flue gas dechlorinating agent in the market is less than 40 percent, and the crushing strength is only about 50N/cm.
The active component of the dechlorinating agent prepared by the domestic blending method is mostly Na 2 CO 3 、NaOH、NaHCO 3 、CaO、CaCO 3 The dechlorinating agent is prepared by mixing, kneading, molding, drying and roasting the oxides, hydroxides and carbonates of alkali metals and alkaline earth metals, wherein part of the products adopt organic amines as active components, and the carriers are mostly cheap and easily-obtained porous substances such as alumina, diatomite, argil and the like, and organic and high-molecular additives are added.
CN101773768A discloses a dry dechlorinating agent for removing HCl from gas and a preparation method thereof. The antichlor is Na 2 CO 3 、CaCO 3 CaO and MgO are active components, cross-linked bentonite is a porous auxiliary agent, methyl cellulose is a foaming agent and an extrusion aid, and the dechlorinating agent is prepared by extrusion molding, drying and roasting. Cross-linked bentoniteThe method uses polyaluminium cations with larger volume to exchange simple cations with smaller volume, so that the pore system is developed and has large specific surface, the specific surface and pore volume of the cross-linked bentonite are both larger than those of non-cross-linked bentonite, and the cross-linked bentonite is used as a pore auxiliary agent of the dechlorinating agent, so that the specific surface of the dechlorinating agent is increased, and the dechlorinating activity and the chlorine volume of the dechlorinating agent are increased. The antichlor made of cross-linked bentonite has pore volume of 0.3-0.4 mL/g and specific surface area of 70m 2 /g-90m 2 The per gram, the crushing strength is 60N/cm-80N/cm, the price is cheaper than that of pseudo-boehmite and a molecular sieve, the preparation process is simple, the dechlorination activity is high, and the low-temperature chlorine penetration capacity is large.
The chlorine capacity of the hydrogen chloride adsorbent containing zinc oxide and alkaline calcium compounds disclosed in US3935259 is 10-35% at a temperature lower than 500 ℃, which discloses that the harsh working conditions of continuous reforming and regeneration cycle gas cannot be met, and zinc contained in the hydrogen chloride adsorbent is easy to sublimate at a high temperature to cause zinc loss and poisoning of a reforming catalyst. US4374654 discloses an activated alumina and molecular sieve adsorbent for removing hydrogen chloride, but is suitable for use at temperatures below 400 ℃. In addition, the basic metal compound assistant is loaded on alumina, and the chlorine capacity of the adsorbent is in the range of 10-20%, so that the adsorbent is suitable for use under normal temperature conditions and cannot meet the continuous reforming and regeneration flue gas conditions.
Therefore, it is very important to develop a high-efficiency dechlorinating agent meeting the working condition of continuously reforming and regenerating the flue gas.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a dechlorinating agent, a preparation method and application thereof, wherein the dechlorinating agent has the advantages of high chlorine capacity, high mechanical strength, long service life, cracking resistance and the like, and meets the working condition of continuously reforming and regenerating flue gas.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a dechlorination agent comprising an active compound, a carrier former, a complexing enhancer;
the active compound comprises an alkaline earth metal compound;
the carrier forming agent comprises alumina, a molecular sieve and minerals;
the composite reinforcing agent comprises calcium carbonate and sodium hydroxide.
In the invention, the composite reinforcing agent with stable components prepared from calcium carbonate and sodium hydroxide can be used as a tackifier of a dechlorinating agent and has an adhesive effect; the composite reinforcing agent is matched with other components of the dechlorinating agent to supplement the whole skeleton of the dechlorinating agent, plays a role in reinforcing in a composite system, enables the dechlorinating agent to have larger specific surface area and pore volume, keeps higher crushing strength and improves the anti-cracking performance. Especially, the high-efficiency removal of chlorine-containing gas and the stable structure can be realized at high temperature (350-600 ℃).
Preferably, the alkaline earth metal compound comprises any one of, or a combination of at least two of, a salt, an oxide or a hydroxide of an alkaline earth metal, wherein typical but non-limiting combinations include: combinations of salts and oxides, combinations of oxides and hydroxides, combinations of salts, oxides and hydroxides, and the like.
Preferably, the alkaline earth metal compound comprises calcium hydroxide and/or calcium oxide.
Preferably, the active compound comprises magnesium oxide and/or zinc oxide, further preferably magnesium oxide.
Preferably, the minerals comprise any one of kaolin, sepiolite or clay, or a combination of at least two thereof, with typical but non-limiting combinations including: combinations of kaolin and sepiolite, sepiolite and clay, kaolin, sepiolite and clay, and the like.
Preferably, the mineral comprises a powdered structure, such as a mineral powder.
Preferably, the alumina comprises a powdered structure, such as alumina powder.
Preferably, the molecular sieve comprises an X-type molecular sieve and/or a Y-type molecular sieve, further preferably an X-type molecular sieve.
Preferably, the alumina comprises pseudo-boehmite.
In the invention, the alumina powder is pseudo-boehmite powder. Pseudo-thin water aluminiumThe stone powder is also called alumina monohydrate, pseudo boehmite, and has a chemical formula of AlOOH. NH 2 O, n =0.08 to 0.62 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, etc.), good peptizing property, strong cohesiveness, high specific surface area, large pore volume, etc., and is a thixotropic gel in a water-containing state. The application of the dechlorinating agent can obtain a dechlorinating agent with a better pore structure.
Preferably, the mass ratio of the calcium carbonate to the sodium hydroxide is (1-3): 1, wherein 1-3 can be 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, etc., and further preferably (1-2): 1.
In the invention, the mass ratio of the calcium carbonate to the sodium hydroxide is (1-3) to 1, and the composite reinforcing agent can better exert the effects of structure regulation and gluing in the optimal range, so that the comprehensive performance of the dechlorinating agent is taken into consideration.
Preferably, the calcium carbonate comprises whisker structures, such as calcium carbonate whiskers.
Preferably, the whiskers of the calcium carbonate have a length of 1 to 40 μm (e.g., 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, etc.), a diameter of 1 to 5 μm (e.g., 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc.), and an aspect ratio of 5 to 20 (e.g., 6, 8, 10, 12, 14, 16, 18, etc.).
The calcium carbonate is in a whisker structure, has a larger length-diameter ratio and higher structural stability and strength, and can be used as a tackifier of a dechlorinating agent and has an adhesive effect when being prepared into a composite reinforcing agent with stable components with sodium hydroxide. The crystal whisker size is concentrated in the range, so that the prepared composite reinforcing agent is more stable, the crystal whisker is uniformly dispersed in the dechlorinating agent to play a role of a skeleton, better strength is achieved, and a good pore structure is kept, so that the reaction gas can be favorably permeated.
Preferably, the calcium carbonate has a purity of 90% to 99%, such as 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc.
Preferably, the mass percentage of the active compound is 10% to 65%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc., based on 100% of the total mass of the dechlorination agent.
Preferably, the mass percentage of the carrier forming agent is 25% to 90%, such as 30%, 40%, 50%, 60%, 65%, 70%, 80%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percentage of the alumina is 10% to 20%, such as 12%, 14%, 16%, 18%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percentage of the molecular sieve is 10% to 15%, such as 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percentage of the mineral substance is 5% -55%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percentage of the composite reinforcing agent is 1% -15%, such as 2%, 4%, 6%, 8%, 10%, 12%, 14% and the like, based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percent of the calcium carbonate is 0.5% -5%, such as 1%, 2%, 3%, 4%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass percent of the sodium hydroxide is 0.5% -5%, such as 1%, 2%, 3%, 4%, etc., based on the total mass of the dechlorinating agent being 100%.
Preferably, the dechlorination agent also comprises other auxiliary agents.
Preferably, the other auxiliary agents comprise methylcellulose and/or sesbania, further preferably a combination of methylcellulose and sesbania.
Preferably, the sesbania comprises a powdered structure, such as sesbania powder.
Preferably, the mass percentage of the methylcellulose is 0-6%, such as 1%, 2%, 3%, 4%, 5%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the sesbania is 0 to 6 mass percent, such as 1%, 2%, 3%, 4%, 5%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the mass ratio of the methyl cellulose to the sesbania is (1-2): 1 (e.g. 1.
Preferably, the total amount of methylcellulose and sesbania is 5% to 12% (e.g., 6%, 7%, 9%, 10%, etc.) of the total mass of the dechlorination agent.
As a preferable technical scheme, the dechlorination agent comprises the following components by taking the total mass of the dechlorination agent as 100 percent:
within the above preferred ranges, the kinds and contents of the raw materials are matched with each other to provide the dechlorinating agent with appropriate pore structure characteristics, increase specific surface area and pore volume, and maintain high crushing strength.
Further, as a preferable technical scheme, the dechlorination agent comprises the following components by taking the total mass of the dechlorination agent as 100 percent:
in a second aspect, the present invention provides a process for preparing a dechlorinating agent according to the first aspect, the process comprising the steps of:
and mixing the active compound, the carrier forming agent and the composite reinforcing agent, forming, drying and roasting to obtain the dechlorinating agent.
Preferably, the preparation method of the composite reinforcing agent comprises the following steps:
mixing calcium carbonate, sodium hydroxide and a solvent, standing to form a suspension to obtain the composite reinforcing agent.
Preferably, the temperature of the mixing is 20-90 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like.
Preferably, the mixing is performed under stirring conditions.
Preferably, the rotational speed of the stirring is 1 to 10r/s, such as 2r/s, 3r/s, 4r/s, 5r/s, 6r/s, 7r/s, 8r/s, 9r/s, and the like.
Preferably, the time of standing is 1-5h, such as 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, and the like.
Preferably, the mass percentage of the solvent is 50% -85%, such as 55%, 60%, 65%, 70%, 75%, 80% and the like, based on the total mass of the composite reinforcing agent being 100%.
Preferably, the solvent comprises water.
Preferably, the active compound and the carrier forming agent are mixed first and the composite enhancer is sprayed into the mixture.
Preferably, the temperature of the spraying is 50-90 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like.
Preferably, the rate of spraying is 0.1-1L/min, such as 0.2L/min, 0.3L/min, 0.4L/min, 0.5L/min, 0.6L/min, 0.7L/min, 0.8L/min, 0.9L/min, and the like.
Preferably, during said spraying, the mixture is stirred.
Preferably, the stirring is at a rate of 1 to 3r/s, such as 1.5r/s, 2r/s, 2.5r/s, 3r/s, and the like.
Preferably, the temperature of the calcination is 300-750 ℃, such as 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ and the like.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Stirring and mixing calcium carbonate, sodium hydroxide and a solvent at the temperature of 20-90 ℃ at the speed of 1-10r/s, standing for 1-5h to form a suspension with the solvent accounting for 50-85% by mass, and obtaining the composite reinforcing agent;
(2) Firstly, mixing an active compound and a carrier forming agent, spraying the composite reinforcing agent into the mixture at the temperature of 50-90 ℃ at the speed of 0.1-1L/min, stirring the mixture at 1-3r/s in the spraying process, then forming, drying and roasting at the temperature of 300-750 ℃ to obtain the dechlorinating agent.
In a third aspect, the invention provides the use of a dechlorinating agent according to the first aspect in a catalytic reforming section for removing hydrogen chloride.
Compared with the prior art, the invention has the following beneficial effects:
(1) The dechlorination agent has the advantages of high chlorine capacity, high mechanical strength, long service life, cracking resistance and the like, and meets the working condition of continuously reforming and regenerating flue gas.
(2) The dechlorination agent disclosed by the invention is simple in preparation process, has very high chlorine capacity and crushing strength under the conditions of high temperature, high water content and high carbon dioxide content of reformed regenerated gas, and has the advantages of high mechanical strength and long service life.
(3) The penetrating chlorine capacity of the dechlorinating agent is more than 32% at 500 ℃, the crushing strength is more than 90N/cm, and in a preferable range, the penetrating chlorine capacity of the dechlorinating agent is more than 52%, and the crushing strength is more than 120N/cm.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In the invention, the information of part of raw materials is as follows:
an X-type molecular sieve: purchased from Suzhou Kaifeng New Material science and technology Limited, under the name NaX raw powder;
y-type molecular sieve: purchased from Oss catalytic materials (Dalian) Co., ltd., under the name NaY raw powder;
calcium carbonate whisker: the length distribution is concentrated between 1 to 40 mu m, the diameter is between 1 to 5 mu m, the length-diameter ratio is between 5 to 20, and the purity is between 90 and 99 percent.
Sesbania powder: purchased from INNOCHEM under the designation SG1;
methyl cellulose: purchased from Aladdin corporation under the designation M112865.
Example 1
The embodiment provides a dechlorination agent, which comprises the following components in parts by weight: 50 parts of calcium hydroxide, 15 parts of pseudo-boehmite, 5 parts of kaolin, 5 parts of X-type molecular sieve, 10 parts of composite reinforcing agent consisting of calcium carbonate whisker and 5 parts of sodium hydroxide, 5 parts of sesbania powder and 5 parts of methyl cellulose.
The dechlorinating agent is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) Preparing an enhancer suspension with the mass ratio of calcium carbonate whiskers to sodium hydroxide being 2; the preparation temperature is 70 ℃, the composite reinforcing agent is prepared by uniformly mixing stirring paddles with the diameter of 20cm at the rotating speed of 10r/s, and after the preparation is finished, the composite reinforcing agent is kept for 5 hours at the constant temperature of 70 ℃ to obtain the composite reinforcing agent;
(2) Weighing raw materials according to the weight, mechanically mixing uniformly, keeping the composite reinforcing agent stable at 70 ℃, spraying the composite reinforcing agent into a mixture consisting of an active compound and a carrier forming agent at the speed of 0.5L/min, and uniformly stirring at the rotating speed of 3r/s; transferring the mixture into a strip extruding machine, kneading the mixture for three times, and extruding the mixture for forming; and (3) curing the extruded strips for 12 hours, drying in an oven, and then roasting in a muffle furnace at the roasting temperature of 500 ℃ for 3 hours to obtain the dechlorinating agent.
Example 2
This example is different from example 1 in that methylcellulose and sesbania powder are not included, and the rest is the same as example 1.
Example 3
This example is different from example 1 in that sesbania powder is not included, and the rest is the same as example 1.
Example 4
This example is different from example 1 in that 10 parts by weight of methylcellulose, excluding sesbania powder, is used, and the rest is the same as example 1.
Example 5
This example is different from example 1 in that methylcellulose is not included, and the rest is the same as example 1.
Example 6
This example is different from example 1 in that 10 parts by weight of sesbania powder is contained without using methylcellulose, and the rest is the same as example 1.
Example 7
The difference between the present example and example 1 is that the parts by weight of calcium carbonate whisker are 5 parts, the parts by weight of sodium hydroxide are 10 parts, and the rest is the same as example 1.
Example 8
The difference between the example and the example 1 is that the weight portion of calcium carbonate whisker is 12.5 parts, the weight portion of sodium hydroxide is 2.5 parts, and the rest is the same as the example 1.
Example 9
This example is different from example 1 in that 7.5 parts by weight of calcium carbonate whiskers and 7.5 parts by weight of sodium hydroxide were used, and the rest was the same as example 1.
Example 10
The difference between this example and example 1 is that the parts by weight of calcium carbonate whiskers are 11.25 parts, the parts by weight of sodium hydroxide is 3.75 parts, and the rest is the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that calcium carbonate whiskers are not included, and the rest is the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that sodium hydroxide is not included and is otherwise the same as example 1.
Comparative example 3
The comparative example is different from example 1 in that calcium carbonate whiskers are not included, the weight part of sodium hydroxide is 15 parts, and the rest is the same as example 1.
Comparative example 4
The comparative example is different from example 1 in that 15 parts by weight of calcium carbonate whiskers are included without sodium hydroxide, and the rest is the same as example 1.
Comparative example 5
This comparative example differs from example 1 in that the composite reinforcing agent was not added, and the rest was the same as example 1.
Performance testing
The dechlorination agents described in examples 1-10 and comparative examples 1-5 were tested as follows:
crushing the dechlorinating agent into particles with a certain mesh number, counting the crushing strength, measuring a certain number of crushed and sieved samples, compacting and filling the crushed and sieved samples into a quartz reaction tube with a certain height-diameter ratio, placing the quartz reaction tube into a customized heating furnace, and adjusting the reaction temperature to 500 ℃; introducing mixed gas (including HCl gas, carbon dioxide, air and the like) into a reaction tube, wherein the gas inlet concentration is 15000ppm, and the gas inlet space velocity is 3000h -1 And adopting a microcomputer coulometer to sample and measure the HCl concentration of tail end outlet gas, and judging penetration when the outlet gas is less than or equal to 0.5 ppm.
The test results are summarized in table 1.
TABLE 1
| Penetrating chlorine capacity, mass% | Crush strength, N/cm | |
| Example 1 | 55 | 128 |
| Example 2 | 32 | 141 |
| Example 3 | 47 | 123 |
| Example 4 | 51 | 99 |
| Example 5 | 44 | 120 |
| Example 6 | 50 | 107 |
| Example 7 | 43 | 90 |
| Example 8 | 40 | 95 |
| Example 9 | 56 | 120 |
| Example 10 | 52 | 130 |
| Comparative example 1 | 32 | 82 |
| Comparative example 2 | 25 | 75 |
| Comparative example 3 | 37 | 83 |
| Comparative example 4 | 28 | 78 |
| Comparative example 5 | 11 | 21 |
The data in the table 1 show that the penetrating chlorine capacity of the dechlorination agent is more than 32% at 500 ℃, the crushing strength is more than 90N/cm, and the dechlorination agent has the advantages of high chlorine capacity, high mechanical strength, long service life, cracking resistance and the like.
As can be seen from the analysis of comparative examples 1-5 and example 1, the performance of comparative examples 1-5 is inferior to that of example 1, and the dechlorinating agent of the invention is proved to be superior to the prior high-temperature regeneration flue gas dechlorinating agent, and the performance of the composite reinforcing agent formed by the coordination of calcium carbonate and sodium hydroxide is better.
As can be seen from the analysis of examples 2-6 and example 1, examples 2-6 are inferior to example 1 in performance, and the dechlorinating agent of the present invention is better in performance when added with methylcellulose and sesbania in a specific ratio.
As is clear from the analysis of examples 7 to 8 and example 1, examples 7 to 8 were inferior in performance to example 1, and from the analysis of examples 9 to 10 and example 1, examples 9 to 10 were similar in performance to example 1, and it was confirmed that the control of the quality of calcium carbonate and sodium hydroxide was better than the performance of the dechlorinating agent formed in the range of (1 to 3): 1.
The present invention is illustrated in detail by the examples given above, but the present invention is not limited to the details given above, which means that the present invention is not limited to the details given above. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A dechlorination agent, which is characterized by comprising an active compound, a carrier forming agent and a compound reinforcing agent;
the active compound comprises an alkaline earth metal compound;
the carrier forming agent comprises alumina, a molecular sieve and minerals;
the composite reinforcing agent comprises calcium carbonate and sodium hydroxide.
2. The dechlorination agent according to claim 1, wherein the alkaline earth metal compound comprises any one of a salt, an oxide or a hydroxide of an alkaline earth metal or a combination of at least two thereof;
preferably, the alkaline earth metal compound comprises calcium hydroxide and/or calcium oxide;
preferably, the mineral comprises any one of kaolin, sepiolite or clay or a combination of at least two thereof;
preferably, the mineral substance comprises a powdery structure;
preferably, the alumina comprises a powdered structure;
preferably, the alumina comprises pseudo-boehmite;
preferably, the molecular sieve comprises an X-type molecular sieve and/or a Y-type molecular sieve.
3. The dechlorination agent according to claim 1 or 2, characterized in that the mass ratio of calcium carbonate to sodium hydroxide is (1-3) 1;
preferably, the calcium carbonate comprises a whisker structure;
preferably, the length of the whisker of the calcium carbonate is 1-40 μm, the diameter is 1-5 μm, and the length-diameter ratio is 5-20;
preferably, the purity of the calcium carbonate is 90% -99%.
4. Dechlorination agent according to any of claims 1 to 3, characterized in that the mass percentage of active compounds is between 10% and 65% with respect to 100% of the total mass of the dechlorination agent;
preferably, the mass percent of the carrier forming agent is 25-90% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the alumina is 10-20% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the molecular sieve is 10-15% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the mineral matters is 5-55% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the composite reinforcing agent is 1-15% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the calcium carbonate is 0.5% -5% based on 100% of the total mass of the dechlorinating agent;
preferably, the mass percent of the sodium hydroxide is 0.5-5% based on 100% of the total mass of the dechlorinating agent.
5. The dechlorination agent according to any one of claims 1 to 4, characterized in that it further comprises other auxiliaries;
preferably, the other auxiliary agents include methylcellulose and/or sesbania;
preferably, the sesbania comprises a powder structure;
preferably, the mass percent of the methyl cellulose is 0-6% based on 100% of the total mass of the dechlorinating agent;
preferably, the sesbania is 0-6% by mass based on 100% by mass of the total dechlorinating agent;
preferably, the mass ratio of the methyl cellulose to the sesbania is (1-2): 1.
6. A process for the preparation of a dechlorination agent according to any one of claims 1 to 5, which process comprises the steps of:
and mixing the active compound, the carrier forming agent and the composite reinforcing agent, forming, drying and roasting to obtain the dechlorinating agent.
7. The preparation method of claim 6, wherein the preparation method of the composite reinforcing agent comprises the following steps:
mixing calcium carbonate, sodium hydroxide and a solvent, and standing to form a suspension to obtain the composite reinforcing agent;
preferably, the temperature of the mixing is 20-90 ℃;
preferably, the mixing is performed under stirring conditions;
preferably, the rotating speed of the stirring is 1-10r/s;
preferably, the standing time is 1-5h;
preferably, the total mass of the composite reinforcing agent is 100%, and the mass percentage of the solvent is 50% -85%;
preferably, the solvent comprises water.
8. The process according to claim 6 or 7, wherein the active compound and the carrier-forming agent are mixed and the composite reinforcing agent is sprayed into the mixture;
preferably, the temperature of the spraying is 50-90 ℃;
preferably, the spraying rate is 0.1-1L/min;
preferably, during the spraying, the mixture is stirred;
preferably, the stirring rate is 1-3r/s;
preferably, the temperature of the calcination is 300-750 ℃.
9. The method according to any one of claims 6 to 8, characterized by comprising the steps of:
(1) Stirring and mixing calcium carbonate, sodium hydroxide and a solvent at the temperature of 20-90 ℃ according to the speed of 1-10r/s, standing for 1-5h to form a suspension with the solvent accounting for 50-85% by mass, and obtaining the composite reinforcing agent;
(2) Firstly, mixing an active compound and a carrier forming agent, spraying the composite reinforcing agent into the mixture at the temperature of 50-90 ℃ at the speed of 0.1-1L/min, stirring the mixture at 1-3r/s in the spraying process, then forming, drying and roasting at the temperature of 300-750 ℃ to obtain the dechlorinating agent.
10. Use of a dechlorinating agent according to any one of claims 1 to 5 for removing hydrogen chloride in a catalytic reforming section.
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