CN116159563A - Desulfurizing and dechlorinating agent, and preparation method and application thereof - Google Patents
Desulfurizing and dechlorinating agent, and preparation method and application thereof Download PDFInfo
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- CN116159563A CN116159563A CN202211683323.6A CN202211683323A CN116159563A CN 116159563 A CN116159563 A CN 116159563A CN 202211683323 A CN202211683323 A CN 202211683323A CN 116159563 A CN116159563 A CN 116159563A
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- calcium
- agent
- compound
- desulfurization
- roasting
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- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 24
- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 73
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 45
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 43
- 230000023556 desulfurization Effects 0.000 claims abstract description 43
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 18
- 229940043430 calcium compound Drugs 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011499 joint compound Substances 0.000 claims abstract description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 13
- 241000219782 Sesbania Species 0.000 claims description 11
- 229920002472 Starch Polymers 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000008107 starch Substances 0.000 claims description 11
- 235000019698 starch Nutrition 0.000 claims description 11
- 239000004927 clay Substances 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 239000000440 bentonite Substances 0.000 claims description 8
- 229910000278 bentonite Inorganic materials 0.000 claims description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- 238000000746 purification Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8659—Removing halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of raw material purification, and particularly relates to a desulfurization and dechlorination agent, and a preparation method and application thereof. The invention provides a desulfurization and dechlorination agent, which comprises the following raw material components: a calcium-iron compound and a calcium-based compound; the iron-calcium compound is obtained by mixing red mud, glacial acetic acid, calcium hydroxide and a pore-expanding agent, molding and roasting; the calcium compound comprises at least one of calcium carbonate and calcium hydroxide. The invention uses the calcium-iron compound and the calcium-series compound as the desulfurizing and dechlorinating agent, which can simultaneously dechlorinating and desulfurizing under the high temperature condition, thereby improving the removal precision.
Description
Technical Field
The invention belongs to the technical field of raw material purification, and particularly relates to a desulfurization and dechlorination agent, and a preparation method and application thereof.
Background
Sulfide is produced in many occasions in industrial production, such as natural gas purification, petroleum smelting, gas production, leather production, pharmacy, paper making, synthetic chemical fiber production and the like, and particularly in the production process of preparing chemical raw materials from coal or petroleum, the raw materials contain more sulfur-containing substances, so that the substances react in the production process to release a large amount of hydrogen sulfide under a high-temperature environment. As the quality of crude oil raw coal decreases, impurity components in raw materials are more and more increased. There are cases where hydrogen sulfide and hydrogen chloride are both present. On the other hand, if the harmful gas is directly discharged, the harmful gas can seriously affect the environment, even cause poisoning of people and animals, and therefore, the harmful gas needs to be removed.
At present, a separate removal mode is generally adopted for removing hydrogen sulfide and hydrogen chloride under the high-temperature condition. The common removal method mainly comprises a dry method and a wet method, in actual industrial production, the application of the dry method removal technology is relatively wide in consideration of the factors such as desulfurization precision, energy consumption, purification cost and the like, the basic principle of the dry method removal is that hydrogen sulfide and hydrogen chloride are adsorbed or reacted into solid sulfur chloride through a solid desulfurizing agent by utilizing gas-solid phase contact reaction, the existing high-temperature desulfurizing agent is mainly zinc oxide desulfurizing agent, ferric oxide or hydroxy iron desulfurizing agent, and the dechlorinating agent is mainly calcium dechlorinating agent. However, the existing desulfurizing agent or dechlorinating agent has poor effects of simultaneously dechlorinating and desulfurizing at high temperature, so that development of a desulfurizing and dechlorinating agent which can simultaneously have excellent dechlorinating and desulfurizing performances at high temperature is urgently needed.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of poor dechlorination and desulfurization effects and low removal precision of the existing desulfurizing agent or dechlorinating agent under the high-temperature condition, thereby providing a desulfurizing and dechlorinating agent, and a preparation method and application thereof.
The invention provides a desulfurization and dechlorination agent, which comprises the following raw material components: a calcium-iron compound and a calcium-based compound;
the iron-calcium compound is obtained by mixing red mud, glacial acetic acid, calcium hydroxide and a pore-expanding agent, molding and roasting;
the calcium compound is at least one selected from calcium carbonate and calcium hydroxide.
Preferably, the mass ratio of the calcium iron compound to the calcium compound is (20-30): (30-45);
the mass ratio of the red mud to the glacial acetic acid to the calcium hydroxide to the pore-expanding agent is 100: (3-5): (50-60): (10-15);
the roasting temperature is 700-1000 ℃ and the roasting time is 1-6h.
Preferably, the molding is extrusion molding, and the step of adding water is further included before the extrusion molding; the invention uses water to adjust the humidity so as to ensure that the squeezing state is achieved;
the roasting step further comprises the step of crushing the roasted product.
Preferably, the composite material comprises the following raw material components in parts by weight: 20-30 parts of calcium iron compound, 30-45 parts of calcium compound, 10-20 parts of sodium salt, 2-15 parts of auxiliary agent and 10-35 parts of clay.
Preferably, the auxiliary agent is selected from at least one of copper salt, magnesium salt and aluminum salt, preferably, the auxiliary agent is selected from copper salt and magnesium salt, the copper salt is copper nitrate, the magnesium salt is magnesium nitrate, and the mass ratio of the copper nitrate to the magnesium nitrate is 1: (0.9-1.1);
the sodium salt is at least one of sodium carbonate and sodium bicarbonate;
the clay is at least one selected from bentonite, attapulgite, diatomite and activated clay;
the pore-expanding agent is at least one selected from starch, methyl cellulose, citric acid and sesbania powder, preferably selected from starch and sesbania powder, and the mass ratio of the starch to the sesbania powder is 3: (1-3).
The invention also provides a preparation method of the desulfurization and dechlorination agent, which comprises the following steps:
mixing the iron calcium compound, the sodium salt and the clay, then mixing and impregnating with the auxiliary agent solution, drying, crushing, forming, drying and roasting to obtain the desulfurization and dechlorination agent.
Preferably, the auxiliary solution is prepared by mixing an auxiliary with water, and the concentration of the auxiliary solution is 0.1-1g/mL.
Optionally, pulverizing to below 100 mesh.
Preferably, the molding step is carried out in a strip extrusion molding mode, and sodium carboxymethyl cellulose solution and crushed materials are mixed before the strip extrusion molding step; the mass concentration of the sodium carboxymethyl cellulose solution is 0.5-2%, and the mass ratio of the crushed material to the sodium carboxymethyl cellulose solution is 1: (0.3-0.4).
Preferably, the soaking time is 2-8 hours;
the drying temperature is 100-120 ℃ and the drying time is 2-8h;
the drying temperature is 100-120 ℃, and the drying time is 2-8 hours;
the roasting temperature is 400-500 ℃ and the roasting time is 1-6h.
The invention also provides an application of the desulfurization and dechlorination agent or the desulfurization and dechlorination agent prepared by the method in desulfurization and dechlorination.
The technical scheme of the invention has the following advantages:
(1) The invention provides a desulfurization and dechlorination agent, which comprises the following raw material components: a calcium-iron compound and a calcium-based compound; the iron-calcium compound is obtained by mixing red mud, glacial acetic acid, calcium hydroxide and a pore-expanding agent, molding and roasting; the calcium compound comprises at least one of calcium carbonate and calcium hydroxide. The invention selects the red mud with high ferric oxide content, glacial acetic acid, calcium hydroxide and pore-enlarging agent to form the calcium-iron compound as the desulfurization active component, and simultaneously ensures that the desulfurization and dechlorination agent has higher mechanical strength, avoids the influence of high temperature on the active component and the situation of blocking holes when the catalyst is melted by hydrogen chloride at high temperature, and improves the high-temperature desulfurization precision. Other substances in the red mud are acidified by glacial acetic acid and calcined at high temperature, and the obtained pure substances have certain effect on dechlorination. The calcium compound is used as the main dechlorination component, and the high-temperature dechlorination agent has the advantages of good high-temperature dechlorination effect, high precision and the like under the condition of higher mechanical strength of the desulfurization dechlorination agent. By adding the pore-expanding agent, the specific surface area of the sample is increased, and the removal effect can be exerted maximally in the removal reaction process. The invention uses the calcium-iron compound and the calcium-series compound as the desulfurizing and dechlorinating agent, which can simultaneously dechlorinating and desulfurizing under the high temperature condition, thereby improving the removal precision.
(2) The invention provides a desulfurization and dechlorination agent, which comprises the following raw material components in parts by weight: 20-30 parts of calcium iron compound, 30-45 parts of calcium compound, 10-20 parts of sodium salt, 2-15 parts of auxiliary agent and 10-35 parts of clay. The sodium salt is added into the desulfurizing and dechlorinating agent, so that the desulfurizing and dechlorinating agent has a higher removal effect on hydrogen chloride at a high airspeed, and the dechlorinating precision can be enhanced. The metal oxide formed by the added auxiliary agent further improves the removal precision of the desulfurization and dechlorination agent.
(3) The preparation method of the desulfurization and dechlorination agent provided by the invention comprises the following steps: mixing the iron calcium compound, the sodium salt and the clay, then mixing and impregnating with the auxiliary agent solution, drying, crushing, forming, drying and roasting to obtain the desulfurization and dechlorination agent. The invention adopts an impregnation mode to add the auxiliary agent, so that a small amount of the auxiliary agent can be fully and uniformly dispersed in the middle of the desulfurization and dechlorination agent, and the function of the auxiliary agent is exerted to the greatest extent. After roasting, the function of a pore-expanding agent is effectively exerted, and the specific surface area of the sample is improved; meanwhile, the strength of the desulfurization and dechlorination agent is enhanced, the desulfurization and dechlorination agent is simultaneously desulfurized and dechlorinated at high temperature, and the removal precision is improved.
(4) The preparation method for preparing the high-temperature desulfurization and dechlorination agent is simple, convenient to operate, capable of realizing large-scale industrial production, low in cost and easy to obtain raw materials, low in production cost, capable of effectively treating red mud, capable of changing waste into valuable, and good in economic benefit and social benefit.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, 9g of starch and 3g of sesbania powder, mixing, adjusting the dryness and the humidity by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium iron compound;
2) 25g of a calcium-iron compound, 30g of calcium carbonate, 10g of sodium carbonate and 33g of bentonite are mixed, immersed into an auxiliary agent solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to below 100 meshes, and crushed materials and a sodium carboxymethyl cellulose solution with the mass concentration of 2% are mixed according to the mass ratio of 1:0.4, mixing, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Example 2
The embodiment provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, 9g of starch and 3g of sesbania powder, mixing, adjusting the dryness and the humidity by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium iron compound;
2) 20g of a calcium-iron compound, 40g of calcium carbonate, 15g of sodium carbonate and 22g of bentonite are mixed, immersed into an auxiliary agent solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to below 100 meshes, and the crushed material and a sodium carboxymethyl cellulose solution with the mass concentration of 1% are mixed according to the mass ratio of 1:0.3, mixing, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Example 3
The embodiment provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, 9g of starch and 3g of sesbania powder, mixing, adjusting the dryness and the humidity by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium iron compound;
2) 30g of a calcium-iron compound, 35g of calcium carbonate, 20g of sodium carbonate and 11g of bentonite are mixed, immersed into an auxiliary agent solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to below 100 meshes, and crushed materials and a sodium carboxymethyl cellulose solution with the mass concentration of 1.5% are mixed according to the mass ratio of 1: mixing 0.35, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Example 4
The embodiment provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, 9g of starch and 3g of sesbania powder, mixing, adjusting the dryness and the humidity by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium iron compound;
2) 25g of a calcium-iron compound, 30g of calcium hydroxide, 10g of sodium bicarbonate and 33g of attapulgite are mixed, immersed into an auxiliary agent solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to below 100 meshes, and crushed materials and a sodium carboxymethyl cellulose solution with the mass concentration of 1.3% are mixed according to the mass ratio of 1: mixing 0.33, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Comparative example 1
The comparative example provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
55g of calcium carbonate, 10g of sodium carbonate and 33g of bentonite are mixed and immersed into an auxiliary solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, the mixture is kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to be less than 100 meshes, and the mass ratio of the crushed material to the sodium carboxymethyl cellulose solution with the mass concentration of 2% is 1:0.4, mixing, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Comparative example 2
The comparative example provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, 9g of starch and 3g of sesbania powder, mixing, adjusting the dryness and the humidity by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium iron compound;
2) 25g of a calcium-iron compound, 10g of sodium carbonate and 33g of bentonite are mixed and immersed into an auxiliary solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, the mixture is kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to be less than 100 meshes, and the crushed material and a sodium carboxymethyl cellulose solution with the mass concentration of 2% are mixed according to the mass ratio of 1:0.4, mixing, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Comparative example 3
The comparative example provides a preparation method of a desulfurization and dechlorination agent, which comprises the following steps:
1) Uniformly mixing 100g of red mud and 3g of glacial acetic acid, adding 55g of calcium hydroxide, mixing, adjusting the dryness and the wetness by using water to reach an extrudable state, extruding strips, forming, roasting at 800 ℃ for 6 hours, and crushing to obtain a calcium-iron compound;
2) 25g of a calcium-iron compound, 30g of calcium carbonate, 10g of sodium carbonate and 33g of bentonite are mixed, immersed into an auxiliary agent solution prepared from 7.6g of magnesium nitrate, 7.1g of copper nitrate and 60ml of water, kept immersed for 2 hours, dried for 2 hours at 120 ℃, crushed to below 100 meshes, and crushed materials and a sodium carboxymethyl cellulose solution with the mass concentration of 2% are mixed according to the mass ratio of 1:0.4, mixing, extruding, forming, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ for 4 hours to obtain the desulfurization and dechlorination agent.
Test case
The products prepared in each example and the products of the comparative examples were subjected to sulfur capacity and pressure tests, and the test results are shown in table 1.
Experimental conditions: the inner diameter of the reaction tube is 10mm, the catalyst size is 20-40 meshes, and the filling amount is 6ml.
The testing method comprises the following steps:
(1) The sulfur capacity investigation method is to use standard gas with the hydrogen sulfide content of 300ppm and the hydrogen chloride concentration of 8000ppm, and the experimental airspeed of 1000h -1 The experimental temperature of 400 ℃ and the outlet hydrogen sulfide or hydrogen chloride concentration of greater than 0.02ppm were considered breakthrough. The tail gas is detected by using a gas detection tube.
Sulfur capacity or chlorine capacity calculation formula: s= (v×c)/M
S: sulfur capacity or chlorine capacity,%;
v: the volume of the gas;
c: h in gas 2 Concentration of S or HCl, mg/m 3 ；
M: the dosage of the desulfurization and dechlorination agent.
(2) The average value of the crushing force of the particle points was measured by using a ZQJ-III intelligent particle strength tester.
TABLE 1
| Sulfur capacity, percent | Chlorine capacity, percent | Strength, N/cm | |
| Example 1 | 10.3 | 37 | 110 |
| Example 2 | 11 | 38.79 | 113 |
| Example 3 | 10.78 | 38.21 | 108 |
| Example 4 | 11.1 | 38.46 | 127 |
| Comparative example 1 | 10.1 | 20.29 | 78 |
| Comparative example 2 | 5.9 | 33.47 | 85 |
| Comparative example 3 | 8.1 | 31.2 | 95 |
From the table: the desulfurizing and dechlorinating agent of the invention is used inHas better pressure intensity at high temperature and can effectively remove H 2 S and HCl. Wherein H is removed under the condition that the outlet precision is controlled to be less than or equal to 0.02ppm 2 The sulfur capacity of S can reach more than 10.3 percent, and the chlorine capacity can reach more than 37 percent.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The desulfurizing and dechlorinating agent is characterized by comprising the following raw material components: a calcium-iron compound and a calcium-based compound;
the iron-calcium compound is obtained by mixing red mud, glacial acetic acid, calcium hydroxide and a pore-expanding agent, molding and roasting;
the calcium compound is at least one selected from calcium carbonate and calcium hydroxide.
2. The desulfurizing and dechlorinating agent according to claim 1, wherein the mass ratio of the calcium-iron compound to the calcium-based compound is (20-30): (30-45);
the mass ratio of the red mud to the glacial acetic acid to the calcium hydroxide to the pore-expanding agent is 100: (3-5): (50-60): (10-15);
the roasting temperature is 700-1000 ℃ and the roasting time is 1-6h.
3. The desulfurizing and dechlorinating agent according to claim 1 or 2, wherein the molding is a bar molding, and the step of adding water is further included before the bar molding;
the roasting step further comprises the step of crushing the roasted product.
4. A desulphurisation and dechlorination agent according to any one of claims 1 to 3 characterised in that it comprises the following raw material components in parts by weight: 20-30 parts of calcium iron compound, 30-45 parts of calcium compound, 10-20 parts of sodium salt, 2-15 parts of auxiliary agent and 10-35 parts of clay.
5. The desulfurizing and dechlorinating agent according to claim 4, wherein the auxiliary agent is at least one selected from copper salt, magnesium salt and aluminum salt, preferably, the auxiliary agent is selected from copper salt and magnesium salt, the copper salt is copper nitrate, the magnesium salt is magnesium nitrate, and the mass ratio of the copper nitrate to the magnesium nitrate is 1: (0.9-1.1);
the sodium salt is at least one of sodium carbonate and sodium bicarbonate;
the clay is at least one selected from bentonite, attapulgite, diatomite and activated clay;
the pore-expanding agent is at least one selected from starch, methyl cellulose, citric acid and sesbania powder, preferably selected from starch and sesbania powder, and the mass ratio of the starch to the sesbania powder is 3: (1-3).
6. A process for preparing the desulfurizing and dechlorinating agent as claimed in any one of claims 1 to 5, comprising the steps of:
mixing the iron calcium compound, the sodium salt and the clay, then mixing and impregnating with the auxiliary agent solution, drying, crushing, forming, drying and roasting to obtain the desulfurization and dechlorination agent.
7. The method according to claim 6, wherein the additive solution is prepared by mixing an additive with water, and the concentration of the additive solution is 0.1-1g/mL.
8. The method according to claim 6, wherein the molding step is performed by extrusion molding, and sodium carboxymethyl cellulose solution is mixed with the crushed material before the extrusion molding step; the mass concentration of the sodium carboxymethyl cellulose solution is 0.5-2%, and the mass ratio of the crushed material to the sodium carboxymethyl cellulose solution is 1: (0.3-0.4).
9. The method of any one of claims 6 to 8, wherein the impregnation time is 2 to 8 hours;
the drying temperature is 100-120 ℃ and the drying time is 2-8h;
the drying temperature is 100-120 ℃, and the drying time is 2-8 hours;
the roasting temperature is 400-500 ℃ and the roasting time is 1-6h.
10. Use of the desulfurization and dechlorination agent according to any one of claims 1 to 5 or the desulfurization and dechlorination agent prepared by the method according to any one of claims 6 to 9 in desulfurization and dechlorination.
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| CN202211683323.6A CN116159563A (en) | 2022-12-27 | 2022-12-27 | Desulfurizing and dechlorinating agent, and preparation method and application thereof |
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| CN202211683323.6A CN116159563A (en) | 2022-12-27 | 2022-12-27 | Desulfurizing and dechlorinating agent, and preparation method and application thereof |
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