CN115400579B - Dechlorination agent and preparation method and application thereof - Google Patents
Dechlorination agent and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006298 dechlorination reaction Methods 0.000 title claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 117
- 230000000382 dechlorinating effect Effects 0.000 claims abstract description 87
- 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 70
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 17
- 229910052801 chlorine Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 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
- 238000000034 method Methods 0.000 claims description 24
- 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
- 238000002156 mixing Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000003623 enhancer Substances 0.000 claims description 6
- 239000000725 suspension Substances 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 150000003839 salts Chemical class 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
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 238000001833 catalytic reforming Methods 0.000 claims description 3
- 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
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 230000035515 penetration Effects 0.000 claims description 2
- 230000000284 resting effect Effects 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 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
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- 235000010981 methylcellulose Nutrition 0.000 description 13
- 239000011148 porous material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000440 bentonite Substances 0.000 description 6
- 229910000278 bentonite Inorganic materials 0.000 description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
- 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
- 239000003463 adsorbent Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 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
- 238000000465 moulding Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 Na 2CO3 Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 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
- 150000001768 cations Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process 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
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process 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
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 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
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 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
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Abstract
The invention relates to a dechlorinating agent, 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 regenerated flue gas.
Description
Technical Field
The invention relates to the technical field of dechlorinating agents, in particular to a dechlorinating agent, a preparation method and application thereof.
Background
In the petroleum refining industry, along with the continuous development of the catalytic reforming process and the continuous improvement of the processing capacity of a reforming device, the hydrogen chloride generated in the working section is also gradually increased, a large amount of organic chloride reacts to generate hydrogen chloride and is combined with water in a system, and the generated highly corrosive hydrochloric acid corrodes equipment, so that the normal production is seriously influenced. Thus, removal of hydrogen chloride is necessary. The existing dechlorinating agent for removing chlorine-containing gas of the reforming device still has unsatisfactory dechlorinating effect in use, insufficient crushing strength, less than 40% of chlorine capacity of the high-temperature flue gas dechlorinating agent existing in the market and only about 50N/cm of crushing strength.
The active components of the dechlorinating agent by the domestic blending method are mostly oxides, hydroxides and carbonates of alkali metals and alkaline earth metals such as Na 2CO3、NaOH、NaHCO3、CaO、CaCO3, part of products adopt organic amines as the active components, and meanwhile, the carriers are mostly porous substances such as alumina, diatomite, carclazyte and the like which are cheap and easy to obtain, and organic and high polymer additives are added, and the dechlorinating agent product is prepared after kneading, molding, drying and roasting.
CN101773768a discloses a dry dechlorinating agent for removing HCl from gas and a preparation method thereof. The dechlorination agent takes Na 2CO3、CaCO3, caO and MgO as active components, crosslinked bentonite as a porous auxiliary agent, methyl cellulose as a foaming agent and an extrusion aid, and is prepared by extrusion molding, drying and roasting. The cross-linked bentonite is simple cation with a relatively large volume and a relatively small volume, so that the pore system is developed, the specific surface area is large, the specific surface area and pore volume of the cross-linked bentonite are relatively large compared with those of non-cross-linked bentonite, and the cross-linked bentonite is used as a pore auxiliary agent of the dechlorination agent, so that the specific surface area of the dechlorination agent is increased, and the dechlorination activity and chlorine capacity of the dechlorination agent are increased. The dechlorination agent prepared from the crosslinked bentonite has the pore volume of 0.3-0.4 mL/g, the specific surface of 70m 2/g-90m2/g and the crushing strength of 60-80N/cm, and the dechlorination agent has the advantages of cheaper price than pseudo-boehmite and molecular sieve, simple preparation process, high dechlorination activity and large chlorine volume of Wen Chuantou.
The hydrogen chloride adsorbent containing zinc oxide and alkaline calcium compound disclosed in US3935259 has chlorine capacity of 10-35% at a temperature lower than 500 ℃, and cannot meet the severe working condition of continuous reforming regeneration circulating gas, and zinc loss is caused by easy sublimation of zinc at high temperature, so that poisoning of reforming catalyst is easily caused. The activated alumina and molecular sieve adsorbents disclosed in US4374654 remove hydrogen chloride but are suitable for use at temperatures below 400 ℃. In addition, the alkali metal compound auxiliary agent disclosed in US4639259 is loaded on alumina, the chlorine capacity of the adsorbent is in the range of 10-20%, and the adsorbent is suitable for being used under normal temperature working conditions and cannot meet the working conditions of continuously reforming and regenerating flue gas.
Therefore, it is important to develop a high-efficiency dechlorinating agent which meets the working condition of continuously reforming and regenerating 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.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a dechlorinating agent comprising an active compound, a carrier shaping agent, 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.
In the invention, the composite reinforcing agent with stable components prepared from the calcium carbonate and the sodium hydroxide can be used as the tackifier of the dechlorinating agent and plays a role in gluing; the composite reinforcing agent is matched with other components of the dechlorinating agent to supplement the integral skeleton of the dechlorinating agent, plays a role in strengthening in a composite system, ensures that the dechlorinating agent has larger specific surface area and pore volume, maintains higher crushing strength, and improves cracking resistance. Particularly, the high-efficiency removal and the stable structure of the chlorine-containing gas can be realized at high temperature (350-600 ℃).
Preferably, the alkaline earth metal compound comprises any one 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: a combination of salts and oxides, a combination of oxides and hydroxides, a combination 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, more preferably magnesium oxide.
Preferably, the mineral comprises any one or a combination of at least two of kaolin, sepiolite or clay, wherein typical but non-limiting combinations include: combinations of kaolin and sepiolite, combinations of sepiolite and clay, combinations of 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, more preferably an X-type molecular sieve.
Preferably, the alumina comprises pseudo-boehmite.
In the invention, the alumina powder is pseudo-boehmite powder. The pseudo-boehmite powder is also called alumina monohydrate or pseudo-boehmite, the chemical formula is AlOOH.nH 2 O, n=0.08-0.62 (for example 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 and the like), and the pseudo-boehmite powder has the characteristics of good peptization performance, strong cohesiveness, high specific surface area, large pore volume and the like, and the water-containing state is thixotropic gel. The application of the dechlorinating agent in the invention can obtain better pore structure.
Preferably, the mass ratio of the calcium carbonate to the sodium hydroxide is (1-3): 1, wherein 1-3 may 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): 1, and the composite reinforcing agent can better bring the structure regulation and the gluing effects into full play in the preferred range, thereby taking the comprehensive performance of the dechlorinating agent into consideration.
Preferably, the calcium carbonate comprises whisker structures, such as calcium carbonate whiskers.
Preferably, the calcium carbonate whiskers 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 dechlorination agent provided by the invention has the advantages that the calcium carbonate is of a whisker structure, has a larger length-diameter ratio and higher structural stability, and can be used as a tackifier of the dechlorination agent and plays a role in gluing when being prepared into a composite reinforcing agent with stable components with sodium hydroxide. The whisker size is concentrated in the above range, so that the prepared composite reinforcing agent is more stable, the 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 maintained, so that the infiltration of reaction gas is facilitated.
Preferably, the purity of the calcium carbonate is 90% -99%, e.g., 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, etc.
Preferably, the mass percentage of the active compound is 10% -65%, e.g. 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the carrier shaping agent is 25% -90% by mass, e.g. 30%, 40%, 50%, 60%, 65%, 70%, 80% etc., based on 100% by mass of the total dechlorinating agent.
Preferably, the alumina is present in a mass percentage of 10% -20%, such as 12%, 14%, 16%, 18%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the molecular sieve is 10% -15% by mass, e.g., 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, etc., based on 100% by mass of the total dechlorinating agent.
Preferably, the mass percentage of the minerals 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 composite enhancer is 1% -15% by mass, e.g., 2%, 4%, 6%, 8%, 10%, 12%, 14% by mass, etc., based on 100% by mass of the total dechlorinating agent.
Preferably, the calcium carbonate is present in a mass percentage of 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 sodium hydroxide is 0.5% -5%, e.g., 1%, 2%, 3%, 4%, etc., based on 100% of the total mass of the dechlorinating agent.
Preferably, the dechlorinating agent further comprises other auxiliary agents.
Preferably, the further auxiliary comprises 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% -6% by mass, e.g. 1%, 2%, 3%, 4%, 5% etc., based on 100% by mass of the total dechlorinating agent.
Preferably, the mass ratio of the methylcellulose to sesbania is (1-2): 1 (e.g. 1:1, 1.2:1, 1.5:1, 1.6:1, 1.8:1 or 2:1, etc.).
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 dechlorinating agent.
As a preferable technical scheme, the dechlorinating agent comprises the following components in percentage by mass based on 100% of the total mass of the dechlorinating agent:
Within the above preferred ranges, the raw material types and contents are mutually matched, so that the dechlorinating agent has proper pore structure characteristics, the specific surface area and the pore volume are increased, and the high crushing strength is maintained.
Further, as a preferable technical scheme, the dechlorinating agent comprises the following components in terms of 100% of the total mass of the dechlorinating agent:
in a second aspect, the present invention provides a method for preparing the dechlorinating agent according to the first aspect, which comprises the following steps:
And mixing the active compound, the carrier forming agent and the composite reinforcing agent, forming, drying and roasting to obtain the dechlorination agent.
Preferably, 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, thereby obtaining the composite reinforcing agent.
Preferably, the temperature of the mixing is 20-90 ℃, e.g., 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, etc.
Preferably, the mixing is performed under stirring conditions.
Preferably, the rotational speed of the stirring is 1-10r/s, e.g. 2r/s, 3r/s, 4r/s, 5r/s, 6r/s, 7r/s, 8r/s, 9r/s, etc.
Preferably, the time of the resting is 1-5 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, etc.
Preferably, the solvent is present in a mass percentage of 50% -85%, such as 55%, 60%, 65%, 70%, 75%, 80%, etc., based on the total mass of the composite enhancer being 100%.
Preferably, the solvent comprises water.
Preferably, the active compound and carrier former are mixed prior to spraying the composite enhancer into the mixture.
Preferably, the temperature of the spray is 50-90 ℃, e.g., 55 ℃, 60 ℃, 65 ℃, 70 ℃,75 ℃, 80 ℃, 85 ℃, etc.
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, etc.
Preferably, during the spraying, the mixture is stirred.
Preferably, the stirring is at a rate of 1-3r/s, such as 1.5r/s, 2r/s, 2.5r/s, 3r/s, etc.
Preferably, the temperature of the calcination is 300-750deg.C, such as 350deg.C, 400deg.C, 450deg.C, 500deg.C, 550deg.C, 600deg.C, 650deg.C, 700deg.C, etc.
As a preferable technical scheme, the preparation method comprises the following steps:
(1) Stirring and mixing calcium carbonate, sodium hydroxide and a solvent at 20-90 ℃ at a speed of 1-10r/s, and standing for 1-5h to form a suspension with the solvent weight percentage of 50% -85%, thereby obtaining the composite reinforcing agent;
(2) Firstly mixing an active compound and a carrier forming agent, then spraying the composite reinforcing agent into the mixture at the speed of 0.1-1L/min at the temperature of 50-90 ℃, stirring the mixture at the speed of 1-3r/s in the spraying process, forming, drying and roasting at the temperature of 300-750 ℃ to obtain the dechlorination agent.
In a third aspect, the present invention provides the use of a dechlorinating agent according to the first aspect for the removal of hydrogen chloride in a catalytic reforming section.
Compared with the prior art, the invention has the following beneficial effects:
(1) 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 regenerated flue gas.
(2) The dechlorination agent provided by the invention has the advantages of simple preparation process, high chlorine capacity and crushing strength under the conditions of high temperature, high water and high carbon dioxide of reformed regenerated gas, high mechanical strength and long service life.
(3) The chlorine penetrating capacity of the dechlorinating agent at 500 ℃ is above 32%, the crushing strength is above 90N/cm, and in a preferred range, the chlorine penetrating capacity of the dechlorinating agent is above 52%, and the crushing strength is above 120N/cm.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the invention, the information of part of raw materials is as follows:
X-type molecular sieve: purchased from the new material technology limited company of Kai, suzhou, with the brand of NaX raw powder;
y-type molecular sieve: purchased from austic catalytic materials (da company) with the brand of NaY raw powder;
calcium carbonate whisker: the length distribution is concentrated between 1 and 40 mu m, the diameter is between 1 and 5 mu m, the length-diameter ratio is between 5 and 20, and the purity is between 90 and 99 percent.
Sesbania powder: purchased from INNOCHEM company under the brand SG1;
Methylcellulose: purchased from Aladin company under the trade name M112865.
Example 1
The embodiment provides a dechlorinating 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 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 a preparation method, which comprises the following steps:
(1) Preparing a reinforcing agent suspension with the mass ratio of calcium carbonate whisker to sodium hydroxide being 2:1, wherein the mass percentage of distilled water in the suspension is 85%; the preparation temperature is 70 ℃, the materials are uniformly mixed by stirring paddles with the diameter of 20cm at the rotation speed of 10r/s, and after the preparation is completed, the materials are kept stand for 5 hours at the constant temperature of 70 ℃ to obtain the composite reinforcing agent;
(2) Weighing the raw materials according to the weight, mechanically mixing uniformly, keeping the composite reinforcing agent stable at 70 ℃ and spraying the composite reinforcing agent into a mixture formed by the active compound and the carrier forming agent at a rate of 0.5L/min, and uniformly stirring at a rotating speed of 3 r/s; transferring into a strip extruding machine, kneading for three times, and extruding strips for molding; and (3) preserving the extruded strips for 12 hours, drying in a drying oven, and then roasting in a muffle furnace, wherein the roasting temperature is 500 ℃ and the time is 3 hours, so as to obtain the dechlorinating agent.
Example 2
This example differs from example 1 in that methylcellulose and sesbania powder are not included, and the remainder is the same as example 1.
Example 3
This example differs from example 1 in that sesbania powder is not included, and the remainder is the same as example 1.
Example 4
This example is different from example 1 in that sesbania powder is not included, 10 parts by weight of methylcellulose is used, and the rest is the same as example 1.
Example 5
This example differs from example 1 in that methylcellulose is not included, and the remainder is the same as example 1.
Example 6
The difference between this example and example 1 is that methylcellulose is not included, 10 parts by weight of sesbania powder is used, and the rest is the same as in example 1.
Example 7
This example differs from example 1 in that the weight part of calcium carbonate whisker is 5 parts, the weight part of sodium hydroxide is 10 parts, and the rest is the same as example 1.
Example 8
This example differs from example 1 in that the weight part of calcium carbonate whisker is 12.5 parts, the weight part of sodium hydroxide is 2.5 parts, and the rest is the same as example 1.
Example 9
This example differs from example 1 in that the weight part of calcium carbonate whisker is 7.5 parts, the weight part of sodium hydroxide is 7.5 parts, and the rest is the same as example 1.
Example 10
This example differs from example 1 in that the weight part of calcium carbonate whisker is 11.25 parts, the weight part 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 no calcium carbonate whisker was included, and the remainder was the same as example 1.
Comparative example 2
This comparative example differs from example 1 in that sodium hydroxide was not included, and the remainder was the same as example 1.
Comparative example 3
This comparative example differs from example 1 in that calcium carbonate whiskers were not included, 15 parts by weight of sodium hydroxide, and the remainder was the same as in example 1.
Comparative example 4
This comparative example differs from example 1 in that sodium hydroxide is not included, the weight part of calcium carbonate whisker is 15 parts, and the rest is the same as example 1.
Comparative example 5
This comparative example differs from example 1 in that no composite reinforcing agent was added, and the remainder was the same as example 1.
Performance testing
The dechlorinating 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, then measuring a certain number of crushed and sieved samples, filling the samples into a quartz reaction tube with a certain height-diameter ratio in a customized heating furnace in a compaction manner, and adjusting the reaction temperature to 500 ℃; and introducing mixed gas (comprising HCl gas, carbon dioxide, air and the like) into a reaction tube, wherein the inlet concentration is 15000ppm, the air inlet airspeed is 3000h -1, sampling and measuring the tail end outlet gas HCl concentration by adopting a microcomputer coulomb meter, 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 content, 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 |
As can be seen from the data in Table 1, the dechlorination agent disclosed by the invention has the advantages of high chlorine capacity, high mechanical strength, long service life, cracking resistance and the like, and penetrates through chlorine capacity at 500 ℃ to be more than 32% and has crushing strength to be more than 90N/cm.
As can be seen from analysis of comparative examples 1-5 and example 1, the performances of comparative examples 1-5 are not as good as those of example 1, and the dechlorination agent disclosed by the invention is better than that of the existing high-temperature regenerated flue gas dechlorination agent, and the composite reinforcing agent formed by matching calcium carbonate with sodium hydroxide is better in performance.
Analysis of examples 2-6 and example 1 shows that examples 2-6 perform less than example 1, demonstrating that the dechlorinating agent of the present invention has better performance when added with methylcellulose and sesbania in specific proportions.
Analysis of examples 7-8 and example 1 shows that examples 7-8 perform less than example 1, and analysis of examples 9-10 and example 1 shows that examples 9-10 perform similar to example 1, demonstrating better control of the dechlorinating agent formed in the mass ratio of calcium carbonate to sodium hydroxide in the range of (1-3): 1.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (39)
1. A dechlorinating agent, which is characterized by comprising 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 calcium carbonate comprises a whisker structure;
the length of the whisker of the calcium carbonate is 1-40 mu m, the diameter is 1-5 mu m, and the length-diameter ratio is 5-20;
The mass ratio of the calcium carbonate to the sodium hydroxide is (1-3) 1;
The chlorine penetration capacity of the dechlorinating agent at 500 ℃ is more than 52%, and the crushing strength is more than 120N/cm.
2. The dechlorinating agent according to claim 1, wherein the alkaline earth metal compound comprises any one or a combination of at least two of a salt, an oxide or a hydroxide of an alkaline earth metal.
3. The dechlorinating agent according to claim 2, characterized in that the alkaline earth metal compound comprises calcium hydroxide and/or calcium oxide.
4. The dechlorinating agent according to claim 1, wherein the mineral comprises any one or a combination of at least two of kaolin, sepiolite or clay.
5. The dechlorinating agent of claim 1, wherein the mineral comprises a powdered structure.
6. The dechlorinating agent of claim 1, wherein the alumina comprises a powdered structure.
7. The dechlorinating agent according to claim 1, wherein the alumina comprises pseudo-boehmite.
8. The dechlorinating agent according to claim 1, characterized in that the molecular sieve comprises an X-type molecular sieve and/or a Y-type molecular sieve.
9. The dechlorinating agent according to claim 1, characterized in that the purity of the calcium carbonate is 90% -99%.
10. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the active compound is 10% -65% based on 100% of the total mass of the dechlorinating agent.
11. The dechlorinating agent according to claim 1, wherein the carrier forming agent is 25-90% by mass based on 100% by mass of the dechlorinating agent.
12. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the alumina is 10-20% based on 100% of the total mass of the dechlorinating agent.
13. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the molecular sieve is 10% -15% based on 100% of the total mass of the dechlorinating agent.
14. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the minerals is 5-55% based on 100% of the total mass of the dechlorinating agent.
15. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the composite reinforcing agent is 1-15% based on 100% of the total mass of the dechlorinating agent.
16. The dechlorinating agent according to claim 1, characterized in that the mass percentage of the calcium carbonate is 0.5% -5% based on 100% of the total mass of the dechlorinating agent.
17. The dechlorinating agent according to claim 1, characterized in that the mass percentage of sodium hydroxide is 0.5% -5% based on 100% of the total mass of the dechlorinating agent.
18. The dechlorinating agent according to claim 1, further comprising other adjuvants.
19. Dechlorinating agent according to claim 18, characterized in that the other auxiliary agent comprises methylcellulose and/or sesbania.
20. The dechlorinating agent according to claim 19, wherein the sesbania comprises a powdered structure.
21. The dechlorinating agent according to claim 19, characterized in that the mass percentage of the methylcellulose is 0-6% based on 100% of the total mass of the dechlorinating agent.
22. The dechlorinating agent according to claim 19, characterized in that the sesbania is 0-6% by mass based on 100% by mass of the total dechlorinating agent.
23. The dechlorinating agent according to claim 19, wherein a mass ratio of the methylcellulose to sesbania is (1-2): 1.
24. A method of preparing a dechlorinating agent as claimed in any one of claims 1 to 23, characterised in that the method 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 dechlorination agent.
25. The method of preparing the composite enhancer of claim 24, comprising the steps of:
mixing calcium carbonate, sodium hydroxide and a solvent, and standing to form a suspension, thereby obtaining the composite reinforcing agent.
26. The method of claim 25, wherein the temperature of the mixing is 20-90 ℃.
27. The method of claim 25, wherein the mixing is performed under stirring.
28. The method of claim 27, wherein the stirring is at a rotational speed of 1-10r/s.
29. The method of claim 25, wherein the time of resting is 1-5 hours.
30. The method of claim 25, wherein the solvent is present in an amount of 50% to 85% by mass based on 100% by mass of the total composite enhancer.
31. The method of claim 25, wherein the solvent comprises water.
32. The method of claim 24, wherein the active compound and carrier forming agent are mixed prior to spraying the composite enhancer into the mixture.
33. The method of claim 32, wherein the spray temperature is 50-90 ℃.
34. The method of claim 32, wherein the spraying is at a rate of 0.1 to 1L/min.
35. The method of claim 32, wherein the mixture is agitated during the spraying.
36. The method of claim 35, wherein the stirring is at a rate of 1-3r/s.
37. The method of claim 24, wherein the firing temperature is 300-750 ℃.
38. The method of any one of claims 24-37, wherein the method of preparation comprises the steps of:
(1) Stirring and mixing calcium carbonate, sodium hydroxide and a solvent at 20-90 ℃ at a speed of 1-10r/s, and standing for 1-5h to form a suspension with the solvent weight percentage of 50% -85%, thereby obtaining the composite reinforcing agent;
(2) Firstly mixing an active compound and a carrier forming agent, then spraying the composite reinforcing agent into the mixture at the speed of 0.1-1L/min at the temperature of 50-90 ℃, stirring the mixture at the speed of 1-3r/s in the spraying process, forming, drying and roasting at the temperature of 300-750 ℃ to obtain the dechlorination agent.
39. Use of a dechlorinating agent as claimed in any one of claims 1 to 23 to remove hydrogen chloride in a catalytic reforming section.
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