CN114130354B - 一种用于低温甲醇洗装置的分子筛及其制备方法 - Google Patents
一种用于低温甲醇洗装置的分子筛及其制备方法 Download PDFInfo
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- CN114130354B CN114130354B CN202111448989.9A CN202111448989A CN114130354B CN 114130354 B CN114130354 B CN 114130354B CN 202111448989 A CN202111448989 A CN 202111448989A CN 114130354 B CN114130354 B CN 114130354B
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000005406 washing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000010457 zeolite Substances 0.000 claims abstract description 33
- 239000004927 clay Substances 0.000 claims abstract description 23
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000008104 plant cellulose Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 29
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 239000001632 sodium acetate Substances 0.000 claims description 12
- 235000017281 sodium acetate Nutrition 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 241000196324 Embryophyta Species 0.000 claims description 4
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052675 erionite Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 229910052678 stilbite Inorganic materials 0.000 claims description 4
- 229920001938 Vegetable gum Polymers 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
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000002734 clay mineral Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 235000009134 Myrica cerifera Nutrition 0.000 claims description 2
- 244000061457 Solanum nigrum Species 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000007789 gas Substances 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000007788 liquid Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- -1 targeted adsorption Chemical compound 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LDZLXQFDGRCELX-UHFFFAOYSA-N 4-phenylbutan-1-ol Chemical compound OCCCCC1=CC=CC=C1 LDZLXQFDGRCELX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000008375 Decussocarpus nagi Nutrition 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000132436 Myrica rubra Species 0.000 description 1
- 235000014631 Myrica rubra Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009102 absorption Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
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- B01J3/04—Pressure vessels, e.g. autoclaves
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明公开了一种用于低温甲醇洗装置的分子筛的制备方法,分子筛的制备材料包括:分子筛原料60‑75%、天然沸石材料15‑20%、高效活性白土15‑20%;植物纤维素粘结剂,所述植物纤维素粘结剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的6‑10%:造孔剂材料,所述造孔剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的7%;通过本申请制备方法得到的分子筛具有最好的吸附分离效果,受热稳定性、耐酸碱性、选择吸附性也有提升。
Description
技术领域
本发明涉及分子筛领域,具体涉及一种用于低温甲醇洗装置的分子筛制备方法。
背景技术
随着国家的经济效益持续发展,工业科技也日渐强大,但面临企业的环境保护,也是国民经济的一项伟大工程,就当前的合成氨生产企业,废水及废气的排放还在不断增长,如果直接排放出废水或废气,容易造成有机物的富集,会对环境与生物造成危害。
发明内容
基于此,本发明的目的在于提供一种,通过这种方法得到的净化剂银负载率高,脱氧效果佳。
为了实现上述目的,本发明提供以下技术方案:
一种用于低温甲醇洗装置的分子筛的制备方法,其特征在于,所述分子筛的制备材料包括:分子筛原料60-75%、天然沸石材料15-20%、高效活性白土15-20%;
植物纤维素粘结剂,所述植物纤维素粘结剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的6-10%:
造孔剂材料,所述造孔剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的7%;
所述分子筛原料为3A、4A、5A、13X的一种或几种;
所述分子筛的制备方法包括以下步骤:
S1、将所有制备材料放入高温蒸馏釜,使用高温水蒸气将植物纤维素粘结剂及造孔剂加热溶解,通过高温蒸汽穿透分子筛原料,至分子筛原料达到半熟基;
S2、向高温蒸馏釜中加入改性助剂,改性助剂添加量为分子筛原料、天然沸石材料及高效活性白土总质量的9%,然后经过24h高温蒸汽穿透分子筛原料,得到交换材料;
S3、待S2得到的交换材料冷却后晾干,晾干后粉碎至少300目,经过筛分、造粒、烘干、活化得到分子筛。
优选地,所述改性助剂:氯化钠、醋酸钠、硫酸钠中的一种或多种。
优选地,所述植物纤维粘结剂为:羧甲基纤维素钠、羟丙基甲苯纤维素、SG田菁植物胶、杨梅胶中的一种或多种。
优选地,得到的分子筛的颗粒状小球直径为1.6-2.5mm,颗粒抗压强度≯35N/颗。
优选地,所述造孔剂为碳酸氢铵,甲基丙酸甲脂、碳酸铵中的一种或几种。
优选地,所述高效活性白土为高温软质粘土矿材料。
优选地,所述天然沸石为斜发沸石、毛沸石、丝光沸石、辉沸石中的一种或几种。
优选地,所述分子筛的制备材料为:
分子筛原料75%、天然沸石材料15%、高效活性白土15%;
植物纤维素粘结剂,所述植物纤维素粘结剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的8%:
造孔剂材料,所述造孔剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的7%;
S3、待S2得到的交换材料冷却后晾干,粉碎至至少320目,再进行对粉碎后的原材料进行筛分,造粒、烘干,然后经高温575℃活化3-6h后,制得分子筛。
有益效果:
本发明公开了一种用于低温甲醇洗装置的分子筛的制备方法,通过这种方法得到的分子筛,吸附效果好,在本发明中沸石经过改性后,孔道结构具有很大的内表面积(560-980m2g),具有最好的吸附分离效果,受热稳定性、耐酸碱性、选择吸附性也有提升。尤其是分子筛的吸收率从每立方吸附N2、H2化合物3.8kg每小时,改性后的沸石分子筛每立方吸附N2、H2中H2O和化合物等增加到6.2kg每小时。
低温甲醇洗装置是将变换后的原料气,在变换系统中用水洗涤,使其中的NH3含量降至1ppm以下。在进行低温甲醇洗系统的原料气先与合成气CO2产品气初步换热后经氨冷却器进一步降温,在原料气分离器初步分离出水份。
低温甲醇洗法是利用低温下-50℃至-60℃,由甲醇的优良特性去脱除原料气中的CO2、H2S、COS等,其物理吸收具有很高效果。但不同的气体在甲醇中溶解度(2CO——40℃),低温下H2S溶解度比CO2大5.5倍。从原料气中分别吸收的H2S、CO2,在解吸再生时也可以分别进行回收。低温下的甲醇溶解活性组份很强,如H2S、COS、CO2比H2大230倍左右。
甲醇液在气体CO2解吸塔上段要闪蒸出所溶解的CO2,同时溶解的H2S部分也被闪蒸出来。从中间闪蒸塔上部出来的不含硫的甲醇液进入气提CO2解吸塔,最上部闪蒸罐,闪蒸气为CO2气,其用来再吸收闪蒸气体中的H2S。
从甲醇洗工序来的原料气首先进入分子筛吸附器,主要脱除CO2、CH3OH、H2S等杂质除去后,在进入氮洗塔顶部来的净化气,从塔底尾液及其闪蒸气来回收氢逆流换热,等冷却到一定温度后再进入继续冷却换热。换热后的气体进入氮洗塔底部,在塔中原料气用液氮洗涤气体中的CO、CH4、Ar等杂质被液氮溶解后得到精制气。从氮洗塔顶部出来经过换热后,对其进行粗配氮,然后进入回收冷量。复热到一定温度后分为两路,一路去甲醇洗工序,经回收冷量后返回液氮洗系统。另一路经氮气冷却器复热后,与甲醇洗工序回来的另一路汇合,送往合成压缩机经压缩后送去合成氨工段。
本发明的主要目的,是提供了一种液氮洗法、甲醇洗分子筛装置中的工艺路线。所述分子筛是采用了有针对性的吸附、分离、解吸、回收等分子筛的联合体作用。
低温甲醇洗的工艺,主要是脱除来自装置中的高沸点物质CO2、CH3OH等。液氮洗脱除工艺中是对氨合成触媒有害作用的CO、CH4、Ar等冷箱组成的惰性气体。由于产品气中的杂质较多,不是一种分子筛就能吸收完的工艺,①是有害气体的分子径大小不同,②是有害气体分为有毒、活性、惰性的三种特性。按常规分子筛是很难长时间达到标准排放要求的。
本发明人经过多次实验结果,基本解决了分子筛的用途提高,产品以被国内合成氨企业在应用中达到肯定。分子筛是采用了合成沸石材料的80%,黏结剂有白土28%,其它纤维粘结剂占少量组份,一经高温活化后,其粘结剂只留下粘结作用,而不占据分子筛的重量比。
两种分子筛吸附孔径是两个层次,一种分子筛只能吸附分子径小于5A的,而另一种分子筛的吸附分子径大于6A以上的;关键是分子筛的作用,一种是吸附作用,对能吸附进去的杂质分子保证在正常操作期间不能随便穿透。另一种是离子交换作用,离子的用量和用途是否正确,在正常操作或再生期间吸而不脱。
对于低温液氮洗法甲醇洗装置中,应用的方法科学性很强,一般通用为:氮氢分离法、离子交换法、生物解吸法、低温再生法等。采用氮氢分离法操作快,效果单一不彻底。离子交换法适用广泛、效果也十分优势,分子筛成本增高。生物解吸法,环保性能最好,分子筛使用较短。低温再生法,表面上看节省了能源,但遇到气体中含水量过高,分子筛再生周期达不到预期使用效果。本发明人坚持离子交换法是选择液氮法和甲醇洗的主要发明依据。
分子筛的原材料PH值最佳间段为7-10之间。这是因为N、H在液氮洗或甲醇洗的操作中分享要平衡,由氢离子随PH值减小,这时N2气的浓度增加,所以分子筛能够吸附较多N2。
本发明的分子筛离子交换性质也是分子筛提高吸脱附效果的主要因素。在制做分子筛的晶格中的空腔中,Na、k、Ca、NaX等阳离子和H2O分子,极易与其周围水溶液里的阴离子发生交换作用,对交换后的沸石分子筛晶格结构更加平衡发达。分子筛经交换后的表现,完全出于离子交换的选择性。
沸石经过改性后,孔道结构具有很大的内表面积(560-980m2g),沸石具有最好的吸附分离效果,特别是改性后的沸石分子筛增加了受热稳定性、耐酸碱性、选择吸附性。尤其是分子筛的吸收率从每立方吸附N2、H2化合物3.8kg每小时,改性后的沸石分子筛每立方吸附N2、H2中H2O和化合物等增加到6.2kg每小时。
本发明的分子筛通过改性后,操作工艺和吸附效果通过静态吸附、动态吸附比较优于常规分子筛16%,低温下的露点优于常规分子筛22%,N2、H2分离效果大于30%,分子筛的总吸附饱和量比常规分子筛每m3大于7.3kg以上。分子筛的穿透温度、压力和时间平均优于常规分子筛的17.4%。改性后的沸石分子筛在使用过程中可以反复再生使用。但对比不同钠盐的分子筛再生效果,选择性也十分重要,在通过分子筛动态吸附对比,用氯化钠、醋酸钠、硫酸钠作为再生后的吸附活性实验结果。氯化钠92%,醋酸钠95%,硫酸钠95.3%。醋酸钠和硫酸钠的对比条件相当。但在价位和安全方面,硫酸钠适合本发明的改性沸石分子筛再生条件与延长剂的组合。本发明的改性分子筛使用寿命大于五年以上。
本发明的分子筛是选择了吸附介质孔径不同的分子筛。沸石分子筛是在国内市场的原材料经过改性后得到的一种用于液氮洗法,甲醇洗的沸石分子筛。材料的选择是采用3A、4A、5A、13X等不同型号的原材料一种或几种。改性的方法和用量是根据吸附不同的分子筛大于脱附及回收不同工艺去完成的,方法是对小分子径杂质吸收采用中孔型吸附剂,对中等级的分子径杂质,选择中上或小于大孔型的吸附剂。然后采取改变分子筛的不同钠盐成分,由Nac1、Na2S04、CH3C00Na、Na2S、NaoH,组成的一种或N种。具体对沸石分子筛改性后的详细描述,由具体实施例中作详细表达。
具体实施方式
为了更好地实施本发明,现作出进一步如下实施例的说明,但实施例不等同对本发明的限制。
现将如下对实施例的具体要求,在本发明专利中作进一步说明。
实施例1
常规材料3A、4A、5A或13X等选出一种或2-3种进行称量配比、喷液等顺序,然后放入高温蒸馏釜使用高温水蒸汽对添加物进行加热溶解,然后在高温蒸汽的热浪穿透中使交换的原材料达到半熟基后,材料的活性组份逐步增强,然后再加入氯化钠9%的量。在经过24小时的热蒸汽反复穿流下,将常规材料中的结晶与新添加材料的结晶熔合为一种四面体,通过氧桥键扩容相连后而形成本实施例所需的分子径。
本实施例的分子筛,由常规材料的3A、4A、5A、13X的一种或几种,用量为60%,作为主要粘结剂的高效活性白土20%,天然高效沸石材料20%,天然沸石为斜发沸石、毛沸石、丝光沸石、辉沸石的一种或几种。植物纤维素粘结剂100:6.5,造孔剂材料100:7的碳酸氢铵,甲基丙酸甲脂、碳酸铵等专用造孔剂的一种或几种。高效活性白土属于高温软质粘土矿材料,其物理性质近似于硅藻土。高温蒸馏釜属于地窖式保温燃气、高温水煮锅,天然气为燃料最高水温可达160℃左右。
装置中的根据吸附分子径选择,两种不同孔径分子筛,一种主要脱除来自甲醇洗原料气中的CO、CH3OH、H2S等杂质,另一种分子筛来自液氮洗原料气中的CO、CH4、Ar等杂质。本实施例的实验结果见下表1。
表1
实施例2
本实施例的原材料,将常规材料的Na型、Ka型、Ca型、Nax型等的一种或几种进行筛分、称量、配比、加入醋酸钠的9%重量、喷液等顺序,然后放入高温蒸馏釜工艺方法同实施例1。
本实施例的分子筛,是由常规原材料的Nax型、Cax型、Kx型组成选择的一种或几种重量为70%,天然高效沸石材料17%,高效白土用量为13%,植物纤维素粘结剂100:10,造孔剂材料100:7的碳酸氢铵、甲基丙烯甲脂、碳酸铵等专用造孔剂的一种或几种。通过高温蒸馏釜的地下水煮锅,使用天然气加热为160℃以上经24h左右交换原材料合成结束。
将上述配料冷却后晾干,粉碎为300目以上,再进行筛分、造粒、然后经高温575℃活化2-4h制成所需分子筛,对分子筛的质量要求于实施例1相同。
装置中所要求的两种不同孔径分子筛:一种是脱除来自液氮洗原料气中的Co、CH4、Ar等杂质,另一种是脱除来自甲醇洗原料气中的:C02、CH30H、H2g等杂质,本实施例,试验结果见下表2:
表2
实施例3
本实施例是在交换后的原材料活性组份逐步增强条件下,添加称量为9%的重量比的硫酸钠,在经过24h的热蒸汽反复穿流中,将常规材料中的结晶与新添加材料中的沸石结晶熔合为一种四面体硅酸盐,通过氧桥键扩容后相连而形成的本实施例所需的两档分子径的专用分子筛。
实施例3是将原常规材料的3A型(ka)、4A型(Na)、5A型(Ca)、13x型(NaX)等,选择一种或几种进行筛分、称量、配比、喷液等顺序,然后按常规材料的75%重量、天然高效沸石材料15%、高效白土用量为10%。植物纤维素黏结剂为:羧甲基纤维素钠、羟丙基甲苯纤维素、SG田菁植物胶、杨梅胶等一种或几种的100:8,造孔剂材料7%(有机类聚甲基丙烯酸酯、甲基丙烯酸甲脂、玉米淀粉等)。(无机类、碳酸铵、碳酸氢铵、氯化铵)等的一种或几种。通过高温蒸馏釜的地槽水煮锅,使用天然气加热至160℃以上,经24h左右交换原材料完成。
本实施例的交换材料冷却后晾干,经粉碎至325目以上,再进行对粉碎后的原材料进行筛分,造粒、烘干,然后经高温575℃活化3-6h后,制得所需分子筛,对分子筛的质量要求于实施例1相同。检测效果体现在下表3。
表3
实施例4
实施例4是在交换后的原材料活性组分逐步增强的条件下。添加称量为3%的醋酸钠、3%氧化钠、3%硫酸钠,合计添加的重量是与实施例1的氯化钠、实施例2的醋酸钠、实施例3的硫酸钠单一重量相同。也是经过24小时的热蒸汽反复穿流后,将常规材料中的结晶与新添加的材料沸石结晶融合为一种四面体硅酸盐。然后再通过氧桥键扩容后相连而形成的本实施例所需的两档分子径的专用分子筛。
本实施例的液氮洗法甲醇洗分子筛的制备方法,将常规使用的分子筛原材料三种A型和一种X型的重量为70%,天然高效沸石材料重量为15%,天然沸石为斜发沸石、丝光沸石、毛沸石、辉沸石等一种或几种。高效活性白土15%为有机物质,选择吸附能力很强的膨润土或硅藻土的一种。植物纤维粘接剂为100:8(CMC)羧甲茎纤维素钠的;(HPMC)羟丙基甲基纤维素;(SG)田菁粉植物胶;(MOL)杨梅栲胶等一种或几种。造孔剂材料100:7,(有机类)聚甲基丙烯。酸脂、甲基丙烯酸甲脂、玉米淀粉等一种或二种,(无机类)碳酸氢铵、氯化铵、碳酸铵等一种或二种。通过高温蒸馏釜160℃以上,24h完成交换。晾干、烘干、焙烧等工艺同实施例3;检测结果见下表4。
表4
实施例5
实施例5,是在交换后的原材料活性组分逐步增强的条件下添加醋酸钠的称量为4.5%、硫酸钠称量为4.5%,合计添加总量与实施例4等重量相同,经过24小时的热蒸汽反复穿流后,将常规材料中的结晶与新添加的材料沸石结晶溶合为一种四面体硅酸盐,然后再通过氧桥键扩溶后相连而形成的本实施例所需要的两档分子径的专用分子筛。
本实施例的分子筛的制备方法和各种原材料的称量比与实施例4相同;对所制成的分子筛通过检测见下表5。
表5
实施例的具体效率,从检测结果中达成,实施例3的制备工艺最实惠,是本发明的最优实施例。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
Claims (1)
1.一种用于低温甲醇洗装置的分子筛的制备方法,其特征在于,所述分子筛的制备材料包括:分子筛原料60-75wt%、天然沸石材料15-20wt%、高效活性白土15-20wt%;
植物纤维素粘结剂,所述植物纤维素粘结剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的6-10%;
造孔剂材料,所述造孔剂的添加量为分子筛原料、天然沸石材料及高效活性白土总质量的7%;
所述分子筛原料为3A、4A、5A、13X的一种或几种;
所述分子筛的制备方法包括以下步骤:
S1、将所有制备材料放入高温蒸馏釜,使用高温水蒸气将植物纤维素粘结剂及造孔剂加热溶解,通过高温蒸汽穿透分子筛原料,至分子筛原料达到半熟基;
S2、向高温蒸馏釜中加入改性助剂,改性助剂添加量为分子筛原料、天然沸石材料及高效活性白土总质量的9%,然后经过24h高温蒸汽穿透分子筛原料,得到交换材料;
S3、待S2得到的交换材料冷却后晾干,晾干后粉碎至少300目,经过筛分、造粒、烘干、活化得到分子筛;
所述改性助剂:氯化钠、醋酸钠、硫酸钠中的一种或多种;
所述植物纤维粘结剂为:羧甲基纤维素钠、羟丙基甲苯纤维素、SG田菁植物胶、杨梅胶中的一种或多种;
所述造孔剂为碳酸氢铵、甲基丙酸甲脂、碳酸铵中的一种或几种;
得到的分子筛的颗粒状小球直径为1.6-2.5mm,颗粒抗压强度≯35N/颗;
所述天然沸石为斜发沸石、毛沸石、丝光沸石、辉沸石中的一种或几种;
所述高效活性白土为高温软质粘土矿材料。
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CN109046237A (zh) * | 2018-09-19 | 2018-12-21 | 江西萍乡市成宇陶瓷有限责任公司 | 一种多选择性吸附分子筛的制备方法 |
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CN109046237A (zh) * | 2018-09-19 | 2018-12-21 | 江西萍乡市成宇陶瓷有限责任公司 | 一种多选择性吸附分子筛的制备方法 |
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