CN113952945B - 一种脱氯剂及其制备方法和应用 - Google Patents
一种脱氯剂及其制备方法和应用 Download PDFInfo
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- CN113952945B CN113952945B CN202111202813.5A CN202111202813A CN113952945B CN 113952945 B CN113952945 B CN 113952945B CN 202111202813 A CN202111202813 A CN 202111202813A CN 113952945 B CN113952945 B CN 113952945B
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- Prior art keywords
- dechlorination
- metal compound
- acid
- molecular sieve
- agent
- Prior art date
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- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 81
- 239000011148 porous material Substances 0.000 claims abstract description 53
- 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 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 52
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003607 modifier Substances 0.000 claims abstract description 22
- 239000001294 propane Substances 0.000 claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 11
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011975 tartaric acid Substances 0.000 claims abstract description 9
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- -1 salt compounds Chemical class 0.000 claims abstract description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 4
- 230000000382 dechlorinating effect Effects 0.000 claims description 48
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 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 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 235000011181 potassium carbonates Nutrition 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 7
- 239000000347 magnesium hydroxide Substances 0.000 claims description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- 239000000057 synthetic resin Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 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 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000460 chlorine Substances 0.000 abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 13
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
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- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B01J20/041—Oxides or hydroxides
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- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
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Abstract
本发明属于脱氯剂制备技术领域,具体涉及一种脱氯剂及其制备方法和应用。其原料包括X型分子筛、碱金属化合物、碱土金属化合物、粘结剂和孔结构改性剂;所述孔结构改性剂为柠檬酸、酒石酸、乙二胺四乙酸、草酸、羧酸或其形成的盐类化合物中的至少一种。本发明以X型分子筛、孔结构改性剂、碱金属化合物、碱土金属化合物和粘结剂作为原料,得到的脱氯剂能够在常温条件下高硫化氢条件下特异性吸附无机氯,该脱氯剂为气相脱氯剂,该脱氯剂尤其是在丙烷脱氢制丙烯产品的脱氯等领域中具有较好的脱氯效果,能够在高硫化氢条件下选择性吸附无机氯,脱氯精度可至0.5ppm以下。
Description
技术领域
本发明属于脱氯剂制备技术领域,具体涉及一种脱氯剂及其制备方法和应用。
背景技术
丙烷储量丰富,而近年来页岩气的开发更是让丙烷的产量进一步上升。目前对丙烷的利用大部分直接进行燃烧供能,极大地降低了其利用价值。将丙烷转化为具有高附加值的产品是提高丙烷利用效率、实现碳基能源高效利用的关键技术之一,具有广阔的实用前景及巨大的经济效益。
在丙烷的下游产品中,丙烯是非常重要的化工原料,可用于生产聚丙烯、丙烯腈、环氧丙烷、乙丙橡胶、尼龙66和ABS树脂等高附加值产品。其中,聚丙烯在人们日常生活应用极广,使得丙烯成为了仅次于乙烯的第二大化工原料。从2012年至2016年,丙烯的产量不断上升,但仍不能满足下游产业对丙烯的需求,可见丙烯下游需求缺口很大。对丙烯需求的不断上升以及页岩气革命副产的大量丙烷为丙烷脱氢技术的发展带来了机遇。
随着丙烷脱氢制丙烯的工艺不断发展,催化剂在反应过程中连续硫化再生,如何在高硫环境下常温特定的脱除丙烷脱氢制丙烯工艺总产物中的总氯并无较好的解决方案。
在现有工艺中,脱除氯化物的方法主要有物理吸附法和化学吸附法两种。例如,现有技术中公开了一种应用于饱和烃和不饱和烃条件下常温气相脱氯剂,该脱氯剂主要以分子筛为载体,主要活性组分为过渡金属二价氧化物(Fe、Ni、Cu、Zn、Mn、Co中的一种或几种组合),但在高硫化氢条件下容易造成该脱氯剂迅速失活,不适用于丙烷脱氢制丙烯工艺。
另外,现有技术中还公开了一种脱氯剂及其制备方法和应用,该脱氯剂主要以分子筛为载体,通过稀土金属对其进行改性,能改变八面沸石分子筛骨架上平衡负电荷的阳离子种类,实现对分子筛酸性、稳定性、吸附性能及孔道结构的调控,但并不能在高硫化氢条件下进行脱氯,也不适用于丙烷脱氢制丙烯工艺。
发明内容
因此,本发明要解决的技术问题在于克服现有技术中的脱氯剂无法在高硫化氢工况下特异性脱出氯化氢的缺陷,从而提供一种脱氯剂及其制备方法和应用。
为此,本发明提供了以下技术方案。
本发明提供一种脱氯剂,其原料包括X型分子筛、碱金属化合物、碱土金属化合物、粘结剂和孔结构改性剂;
所述孔结构改性剂为柠檬酸、酒石酸、乙二胺四乙酸、草酸、羧酸或其形成的盐类化合物中的至少一种。
可选的,所述X型分子筛的硅铝摩尔比为(1.0-1.5):1。
可选的,所述X型分子筛的比表面积为400m2/g-900m2/g,平均孔径为0.7nm-1.5nm。
可选的,包括如下重量份的原料,10-50份X型分子筛、1-20份碱金属化合物、10-40份碱土金属化合物、10-50份粘结剂和0.5-10份孔结构改性剂。
可选的,所述碱金属化合物为碳酸钾,氢氧化钾,碳酸钠,氢氧化钠,碳酸氢钠,碳酸氢钾中的至少一种;
所述碱土金属化合物为氢氧化镁,碳酸镁,碳酸钙,氢氧化钙,碳酸氢钙中的至少一种。
可选的,所述粘结剂为田菁粉,凹凸棒土,高岭土,合成树脂,淀粉,聚乙烯醇,硅溶胶,铝溶胶,羧甲基纤维素钠中的至少一种。
本发明对于粘结剂没有特殊要求,均为本领域常用粘结剂,可通过市售渠道获取。例如,合成树脂为具有粘结环氧树脂、聚氨酯树脂、聚酯树脂中的至少一种;
本发明还提供了一种所述脱氯剂的制备方法,包括以下步骤,
将X型分子筛、碱金属化合物、碱土金属化合物、粘结剂和孔结构改性剂混合均匀,经成型、干燥、焙烧,得到脱氯剂。
可选的,所述焙烧的温度为170-550℃,时间为2-6h。
可选的,所述干燥的温度为100-120℃,时间为2-6h;
本发明还提供了一种上述脱氯剂或上述制备方法制得的脱氯剂在丙烷脱氢制丙烯中的应用。
所述脱氯剂在硫化氢浓度为40-100ppm,对丙烷脱氢制丙烯总产物的总氯进行脱除时,脱除温度为20-60℃,脱除压力为常压至1.5Mpa。
本发明技术方案,具有如下有点:
1.本发明提供的脱氯剂,其原料包括X型分子筛、碱金属、碱土金属、粘结剂和孔结构改性剂;所述孔结构改性剂为柠檬酸、酒石酸、乙二胺四乙酸、草酸、羧酸或其形成的盐类化合物中的至少一种。本发明以X型分子筛、孔结构改性剂、碱金属、碱土金属和粘结剂作为原料,得到的脱氯剂能够在下高硫化氢条件下特异性吸附无机氯,该脱氯剂为气相脱氯剂,该脱氯剂尤其是在丙烷脱氢制丙烯等领域中具有较好的脱氯效果,能够在高硫化氢条件下选择性吸附无机氯,脱氯精度可至0.5ppm以下。具体地,利用X型分子筛骨架的多微孔的孔道结构提高脱除反应的内扩散性,使得到的脱氯剂具有较好的吸附性;在氯化氢环境下,因吸附硫化氢生成的硫化物会同氯化氢反应而不断地向氯化物转化,同时脱附出硫化氢,达到特异性吸附氯化氢的效果,提高脱除反应的选择性。通过在脱氯剂中加入孔结构改性剂,使得到的脱氯剂的介孔孔径、孔容提高,整体孔径分布多样化,可以提高脱氯剂的反应活性,更好的促进氯化物的脱除和转化,有机酸可以促进载体粒子间的相互作用,提高整体的破碎强度,减少粉化和板结的发生,有效的延长了脱氯剂的使用寿命。
本发明提供的脱氯剂,该分子筛的比表面积为400m2/g-900m2/g,孔径为0.7nm-1.5nm,气相中氯化氢分子直径为0.34nm,通过采用具有大比表面积的分子筛可以使氯化氢分子更好的在载体内部扩散,增大内表面的吸附能力,同时有助于氯化氢与活性组分之间的反应,使氯化物脱除完全,提高脱氯精度。
本发明提供的脱氯剂的制备方法,可以提高脱氯剂的破碎强度,提高使用寿命;其中,通过限定焙烧温度可使孔结构改性剂分解,产生介孔孔道结构,防止温度过低杂质堵塞孔道,温度过高载体骨架结构塌陷,活性组分聚集。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例1所得脱氯剂的孔径分布图。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
为了便于数据之间的对比,本发明实施例1-4、对比例1和对比例3用到的分子筛为X型分子筛,分子筛中的硅铝摩尔比为1.28:1,实施例5-6用到的分子筛为低硅铝比X型分子筛(LSX),分子筛中的硅铝摩尔比为1.02:1,实施例7用到的分子筛为X型分子筛,分子筛中的硅铝摩尔比为1.5:1。
田菁粉由抚顺圣飞化工有限公司提供;凹凸棒土由明光市利源粉体材料厂提供;高岭土由沈阳联朋提供;合成树脂采用环氧树脂;干淀粉由国药提供;聚乙烯醇由Aladdin厂家提供,为低黏度,黏度值4.2-5.0的聚乙烯醇;硅溶胶由淄博厂家提供,二氧化硅浓度为30.2%;铝溶胶由济南提供,氧化铝浓度为10%。
实施例1
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为0.7nm的X型分子筛,10g碳酸钾,30g氢氧化镁,5g田菁粉,35g硅溶胶,10g高岭土与5g草酸混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h得气相脱氯剂。
所得脱氯剂的孔径分布图如图1所示,从图中可以看出,其介孔孔径主要分布在3-4nm和6-50nm,同时,还在50nm以上有孔分布,整体孔径分布多样化化;其它实施例和对比例的附图不再提供,仅给出介孔的孔径分布。
实施例2
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为900m2/g,孔径为1.0nm的X型分子筛的分子筛,20g碳酸钠,10g碳酸钠,20g凹凸棒与5g酒石酸混合均匀,加入25g硅溶胶滚球成型,在110℃下干燥3h,再在350℃下焙烧6h得气相脱氯剂。
实施例3
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为400m2/g,孔径为1.2nm的X型分子筛的分子筛,5g氢氧化钠,35g氢氧化钙,3g羧甲基纤维素钠和10g乙二胺四乙酸二钠混合均匀,加入35g硅溶胶滚球成型,在120℃下干燥4h,再在550℃下焙烧4h得气相脱氯剂。
实施例4
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将10g比表面积为500m2/g,孔径为1.5nm的X型分子筛的分子筛,40g碳酸镁,20g碳酸氢钠,20g干淀粉,5g田菁粉,1g酒石酸钾与50g硅溶胶混合均匀,挤条成型后在120℃下干燥6h,再在480℃下焙烧5h得气相脱氯剂。
实施例5
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为1.0nm的X型分子筛的分子筛,10g碳酸氢钠,30g碳酸钙,5g柠檬酸,10g田菁粉,10g高岭土与30g硅溶胶混合均匀,挤条成型后在110℃下干燥3h,再在380℃下焙烧4h后得气相脱氯剂。
实施例6
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为500m2/g,孔径为0.8nm的X型分子筛的分子筛,15g碳酸钾,35g碳酸镁,10g柠檬酸钠,20g硅溶胶,5g田菁粉混合均匀,挤条成型后在110℃下干燥2h,再在350℃下焙烧2h后得气相脱氯剂。
实施例7(硅铝比在1.5的X型分子筛)
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为0.85nm的X型分子筛,10g碳酸钾,30g氢氧化镁,5g田菁粉,35g硅溶胶,10g高岭土与5g草酸混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h得气相脱氯剂。
对比例1
本对比例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为1.0nm的X型分子筛的分子筛,30g氢氧化镁,10g碳酸钾,5g田菁粉,35g硅溶胶与15g高岭土混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h后得气相脱氯剂。
对比例2
本对比例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为1.0nm的高硅铝比(硅铝摩尔比40:1)ZSM-5分子筛,30g氢氧化镁,10g碳酸钾,5g田菁粉,35g硅溶胶,15g高岭土与5g草酸混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h后得气相脱氯剂。
对比例3
本对比例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为1.0nm的X型分子筛的分子筛中加入30g氧化铜,10g碳酸钾,5g田菁粉,35g硅溶胶,15g高岭土与5g草酸混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h后得气相脱氯剂。
对比例4(与实施例1相比,包括其它造孔剂)
本实施例提供了一种脱氯剂的制备方法,包括以下步骤,
将50g比表面积为650m2/g,孔径为1.0nm的X型分子筛,10g碳酸钾,30g氢氧化镁,5g田菁粉,35g硅溶胶,10g高岭土与5g碳酸氢铵混合均匀,挤条成型后在100℃下干燥2h,再在480℃下焙烧3h得气相脱氯剂。
试验例
本试验例提供了一种实施例和对比例制备得到的脱氯剂的性能测试及测试结果。
脱氯剂的脱氯效果评价方法:配置模拟气,模拟气中的氯化氢浓度为10ppm,硫化氢的浓度为100ppm,采用氮气作为平衡气;将实施例1-7和对比例1-4得到的脱氯剂分别置于反应器中,脱氯剂的装填量为15ml,在40℃,常压下反应,反应器的内径为20mm;具体评价步骤包括,将模拟气钢瓶中的模拟气导出,经过浮子流量计调节反应空速后输送至反应器与脱氯剂反应,反应后的气体经过尾气处理后排放;其中,采用日本GASTEC气体检测管对入口硫化氢与氯化氢、出口硫化氢与氯化氢浓度进行测试,采用瑞士万通905(905Titrando)型自动电位滴定仪对反应后的脱氯剂中的氯含量进行测试;实施例1-7和对比例1-4的脱氯剂脱氯后的模拟气中的硫化氢浓度与脱氯剂中的氯含量如表1。
表1实施例1-7和对比例1-4得到的脱氯剂的氯含量与出口硫化氢浓度
从表1中可以看出,实施例1和实施例5可以看出,优化分子筛的硅铝比有助于提高脱氯剂的脱氯效果。实施例1和实施例6相比,可以看出,通过优化原料的配比,可以进一步提高脱氯剂的脱氯效果。实施例1与对比例1相比,可以说明,加入孔结构改性剂可以提高脱氯剂的脱氯效果。实施例1、实施例7与对比例2对比,可以说明,使用更高的硅铝比的分子筛得到的脱氯剂的脱氯效果差。实施例1与对比例3对比,可以说明,过渡金属二价氧化物在高硫化氢环境下对氯化氢吸附效果差而实施例得到的脱氯剂可以对氯化氢选择性吸附。本发明通过使用特定骨架结构的分子筛负载碱金属碱土金属化合物可以实现在硫化氢环境下对氯化氢的选择性吸附,通过优化分子筛、孔结构改性剂,碱金属、碱土金属和粘结剂以及分子筛的比表面积,有助于进一步提高脱氯剂的脱氯效果。
实施例1-7与对比例1-4制得的脱氯剂孔径分布、孔容、破碎强度的测试方法如下:
孔径分布与孔容采用美国麦克默瑞提克(Micromeritics)ASAP 2460自动比表面与孔隙度分析仪进行测试;破碎强度采用大连智能试验机厂ZQJ-Ⅲ智能颗粒强度试验机测试。
孔径分布多样化、孔容、破碎强度测试结果如表2。
表2实施例1-7与对比例1-4的孔径分布、孔容与强度测试数据
由实施例1-7,对比例2可以看出,添加孔结构改性剂可以明显提高脱氯剂的孔径分布范围,尤其是在介孔范围内(2-50nm)出现明显的孔道结构,且呈双峰分布,同时具有良好的破碎强度,而通过对比例1可以看出,未添加孔结构改性剂则在介孔范围内没有广泛的孔径分布,孔容也更小,通过对比例4看出,添加其他种类的孔结构改性剂尽管产生了少量的介孔,但破碎强度低,无法满足丙烷脱氢脱氯的工况要求。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (7)
1.一种脱氯剂在丙烷脱氢制丙烯产品脱氯中的应用,其特征在于,所述脱氯剂的原料包括X型分子筛、碱金属化合物、碱土金属化合物、粘结剂和孔结构改性剂;
所述孔结构改性剂为柠檬酸、酒石酸、乙二胺四乙酸、草酸、羧酸或其形成的盐类化合物中的至少一种;
所述脱氯剂的制备方法,包括以下步骤:
将X型分子筛、碱金属化合物、碱土金属化合物、粘结剂和孔结构改性剂混合均匀,经成型、干燥、焙烧,得到脱氯剂;
所述焙烧的温度为180-550℃,时间为2-6h。
2.根据权利要求1所述的应用,其特征在于,所述X型分子筛的硅铝摩尔比为(1.0-1.5):1。
3.根据权利要求1所述的应用,其特征在于,所述X型分子筛的比表面积为400m2/g-900m2/g,平均孔径为0.7nm-1.5nm。
4.根据权利要求1所述的应用,其特征在于,包括如下重量份的原料,10-50份X型分子筛、1-20份碱金属化合物、10-40份碱土金属化合物、10-50份粘结剂和0.5-10份孔结构改性剂。
5.根据权利要求1所述的应用,其特征在于,所述碱金属化合物为碳酸钾,氢氧化钾,碳酸钠,氢氧化钠,碳酸氢钠,碳酸氢钾中的至少一种;
所述碱土金属化合物为氢氧化镁,碳酸镁,碳酸钙,氢氧化钙,碳酸氢钙中的至少一种。
6.根据权利要求1所述的应用,其特征在于,所述粘结剂为田菁粉,凹凸棒土,高岭土,合成树脂,淀粉,聚乙烯醇,硅溶胶,铝溶胶,羧甲基纤维素钠中的至少一种。
7.根据权利要求1所述的应用,其特征在于,所述干燥的温度为100-120℃,时间为2-6h。
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