CN114367303B - 一种脱有机氯催化剂及其制备方法、应用 - Google Patents
一种脱有机氯催化剂及其制备方法、应用 Download PDFInfo
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000000460 chlorine Substances 0.000 title claims abstract description 75
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 15
- 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 15
- 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 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 12
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 12
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 abstract description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 229960003750 ethyl chloride Drugs 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 42
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 42
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
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- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 208000033830 Hot Flashes Diseases 0.000 description 1
- 206010060800 Hot flush Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- NARWYSCMDPLCIQ-UHFFFAOYSA-N ethane;hydrochloride Chemical compound Cl.CC NARWYSCMDPLCIQ-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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Abstract
本发明公开了一种脱有机氯催化剂制备方法及其应用。该脱有机氯催化剂包含1%‑35%的活性氧化铝、1%‑25%的活性炭、1%‑15%的水滑石和30%‑80%的分子筛其余为助剂。催化助剂为Na、Cs、Ca、Cu、Zn、Fe、Ce中的一种或多种。组分含量为0.1%‑10%。该脱有机氯催化剂孔容为0.5‑1.0cm3/g、比表面积为200‑600m2/g。该脱有机氯催化剂针对化工原料、产品中氯甲烷、二氯甲烷、氯乙烷、二氯乙烷等有机氯杂质的脱除效果明显。可将有机氯脱至0.1ppm以下,同时可将原料中的无机氯降至0.1ppm以下。该脱有机氯催化剂有机氯氯容大,吸附饱和时可再生,再生效果好,有机氯氯容可恢复99%。可以再生1‑8次,再生方法简单,有效满足化工行业低碳烃类净化脱除有机氯的需求。
Description
技术领域
本发明属于催化剂技术领域,涉及一种脱有机氯催化剂及其制备方法、应用。
背景技术
近年来国内丙烯工业发展迅速,2019年,国内新增丙烯产能达到3.66Mt,同比增长10.6%。在新增产能中,传统石化路线占比明显下降,新兴工艺产能增长迅猛,占新增产能的81.15%。当前全球乙烯原料多元化和轻质化发展趋势明显,采用乙烷等轻烃制乙烯将成为趋势,传统路径石脑油裂解副产的丙烯产量增速将趋缓,丙烷脱氢(PDH)或将成为未来丙烯扩能的主要方向。PDH工艺有着原料单一、流程短、丙烯收率高、投资成本低、经济性高等优势。
传统石化路线的催化裂化和蒸汽裂解联产仍是国内丙烯生产的主流,但以煤/甲醇为原料的CTO/MTO路线和以丙烷为原料的PDH路线发展迅速[1]。截至2019年底,国内传统石化路线丙烯产能占比57.7%,煤/甲醇制烯烃路线丙烯产能占比24.4%,PDH/MDH路线丙烯产能占比为17.6%。2019年8月国内首个进口乙烷轻烃综合利用项目投产,轻烃综合利用路线丙烯产能从无到有,占据总产能的0.3%。
传统路径中,丙烯主要来源于石脑油蒸汽裂解、催化裂化(FCC)副产。随着美国页岩气革命的成功,全球乙烯原料多元化和轻质化发展趋势明显,乙烷供给量大增,乙烷裂解制乙烯迎来投产高峰。采用乙烷等轻烃制乙烯将成为趋势,而轻质原料裂解所带来的最大问题是丙烯产量大幅减少,市场供应紧张。传统路径石脑油裂解副产的丙烯产量增速将趋缓。2019年国内丙烯产能扩张维持在10%左右,产能仍处于扩张期,未来原料轻质化进程加剧,丙烷脱氢将成为未来丙烯扩产的主要方向。
目前工业上常用的丙烯生产工艺有传统石化路线的蒸汽裂解和FCC、煤化工路线的CTO和甲醇制烯烃/甲醇制丙烯(MTO&MTP)以及油气路线的丙烷脱氢等工艺。
蒸汽裂解技术以石脑油等为原料,在高温条件下和水蒸气发生分子链断裂和脱氢反应,以制取乙烯和丙烯等低分子烯烃。但该工艺主产乙烯,丙烯是副产品。尽管降低裂解深度可增产丙烯,但丙烯/乙烯比不宜超过0.65,否则会因烯烃收率下降而影响整体经济性。近几年全球受到美国页岩气革命的冲击,乙烷供应大增,价格低廉,蒸汽裂解制乙烯路径受到限制,产能增速趋缓,进而导致丙烯产量随之降低。炼油厂丙烯主要来自FCC,深度催化裂解(DCC)副产,是丙烯的第二大来源。汽柴油过剩,多产丙烯成为一个方向。
CTO包含煤制甲醇和甲醇制烯烃两个过程。MTO&MTP则是以煤制甲醇或外购甲醇为原料,生产低碳烯烃和丙烯的化工技术。近十年来,国内大力发展煤化工,包括煤制烯烃、煤制油、煤制天然气等项目。目前煤制烯烃技术已经完全实现国产化,但仍存在投资强度大,高度依赖水、煤资源等问题。PDH生产工艺将丙烷经过脱氢催化反应制丙烯,副产氢气,该反应是可逆的强吸热过程,可在高温和低压时获得合理的丙烯收率,一般其原料丙烷与产出丙烯比例为1.2:1。PDH装置比其他路线具有一定的成本优势。
丙烷脱氢制丙烯技术经过20多年来的不断发展完善,工业应用日趋成熟。目前,全球丙烷脱氢制丙烯工艺主要有UOP公司的Oleflex工艺、鲁姆斯(Lummus)公司的Catofin工艺、伍德(Uhde)公司的Star工艺、林德(Linde)公司的PDH工艺、Snamprogetti-Yarsintez公司联合开发的FBD工艺等。工业上应用较广的丙烷脱氢工艺是UOP公司的Oleflex工艺与鲁姆斯(Lummus)公司的Catofin工艺。使用的催化剂主要为Pt系和Cr系。
丙烷脱氢工艺在国内发展历史比较短,但发展势头迅猛。2013年10月,国内首套丙烷脱氢装置--天津渤化600kt/a丙烷脱氢装置投产,标志着丙烷脱氢大幕在国内正式拉开,接下来几年呈现出了爆发式增长。随着2019年1月卫星石化(二期)450kt/a PDH装置投产、10月巨正源股份600kt/a PDH装置投产,国内已投入运行的PDH装置共有10套,总产能达到5.66Mt/a。
在国内经济持续增长的背景下,丙烯需求将保持稳定增长。未来一段时间,丙烯原料多元化发展将成为产业的发展趋势。多样化生产路线将齐头并进,传统石化路线仍是主流,但份额逐渐减少。在盈利状况持续较好的情况下,PDH行业掀起了新一轮的投资热潮并伴有过热迹象。未来随着原料轻质化进程加剧,PDH将成为丙烯扩产的主要方向。预计2024年底,国内PDH/MDH产能将达14.00Mt/a左右,占国内总产能的26%,将对国内丙烯产业格局带来新的变化。
UOP公司的Oleflex丙烷脱氢工艺贵金属催化剂再生时,为使贵金属Pt在Al2O3载体孔道表面再分散,需要注入适量的氯。氯源主要包括氯气和一氯乙烷、二氯乙烷等。催化剂再生注氯,使得产物丙烯中含有微量的氯,一般在5ppm以下,影响产物丙烯的品质和应用。为提高丙烯品质和纯度,丰富其应用领域。需要对其含有的微量氯进行脱除。普通HCl的脱除一般使用活性炭和/或Al2O3基吸附剂。掺杂适量碱金属、碱土金属、Fe、Cu等元素,脱除效果明显。
四川润和催化新材料股份有限公司公开的一种有机氯脱除剂及其制备方法与应用(专利号:CN201911367634.X)提供了一种高效可再生的有机氯脱除剂及其制备方法,合理利用工业分子筛废渣和催化平衡剂制备有机氯脱除剂,既解决了当今分子筛工业废渣堆积的难题,又能解决原油加工过程中,因氯含量超标带来的诸多棘手问题。
东营科尔特新材料有限公司公开的脱氯吸附剂及其制备方法、再生方法和脱有机氯的应用(专利号:CN202010337937.3)提供一种在烷基化油中有机氯脱除中的应用的脱氯吸附剂及其制备方法、再生方法。
由于丙烯、异丁烯等低碳烃分子小,与有机氯分子大小相近,至今为止对丙烯中有机氯的脱除没有公开更科学、易操作的办法。
发明内容
为解决上述问题,基于现有技术存在的缺陷,本发明旨在提供一种制备方法及其应用。本发明的目的在于提供一种选择性好、氯容量高、穿透时间长、使用及再生条件简单的脱除丙烯、异丁烯等低碳烃中有机氯的脱有机氯催化剂。
本发明脱有机氯催化剂以催化剂总质量计,包括质量百分含量的下列组分:1%-35%的活性氧化铝、1%-25%的活性炭、1%-15%的水滑石、30%-80%的分子筛。
优选地,包含5%-30%活性氧化铝;
优选地,包含5%-20%活性炭;
优选地,包含5%-10%水滑石;
优选地,包含35%-75%分子筛,所述分子筛为ZSM-5、ZSM-35等。
优选还包含催化助剂,选自Na、Cs、Ca、Cu、Zn、Fe、Ce中的一种或多种,组分含量为0.1%-10%,优选为0.5%-8%。
本发明所述的脱有机氯催化剂,优选包含5%-30%的活性氧化铝、5%-20%的活性炭、1%-15%的水滑石、30%-80%的分子筛。
本发明所述的脱有机氯催化剂,优选脱有机氯催化剂孔容为0.2-1.5cm3/g、比表面积为200-800m2/g。进一步优选地,该脱有机氯催化剂孔容为0.5-1.0cm3/g、比表面积为250-600m2/g。
本发明还进一步提供了上述脱有机氯催化剂的一种制备方法,包括:
将活性氧化铝、活性炭、水滑石、分子筛混合均匀后磨成混合物微粒,然后将混合物微粒加入粘结剂混合、成型,再经干燥、焙烧后制得。
本发明还进一步提供了上述含化学助剂的脱有机氯催化剂的一种制备方法,包括:将活性氧化铝、活性炭、水滑石、分子筛混合均匀后磨成混合物微粒,然后将混合物微粒加入粘结剂、催化助剂盐溶液混合、成型,再经干燥、焙烧后制得。
本发明还提供了上述脱有机氯催化剂在对化工原料净化脱除有机氯杂质中的应用,采用本发明脱有机氯催化剂进行脱除处理后,有机氯含量为0.1ppm以下。有机氯杂质包括氯甲烷、二氯甲烷、氯乙烷、二氯乙烷等有机氯杂质。本发明脱有机氯催化剂有机氯氯容大,吸附饱和时可再生,再生效果好,有机氯氯容可恢复99%。
本发明所述的该脱有机氯催化剂可以再生1-8次,优选可再生生1-5次。
本发明与现有技术相比,具有如下的优点和有益效果:
1)本发明利用活性氧化铝、活性炭、分子筛等的特殊孔道结构和水滑石的层状结构,利于一氯甲烷、一氯乙烷、二氯甲烷、二氯乙烷等有机氯分子的吸附和脱附,选择性高。
2)本发明适用于液相丙烯、气相丙烯、液相丁烯、气相丁烯等低碳烃类中有机氯的脱除,脱除精度高,可将有机氯脱至0.1ppm以下。
3)本发明催化剂制备方法简单、可循环再生,可以再生1-8次,且再生效果好,有机氯氯容可恢复99%,使用寿命长。
4)本发明脱有机氯催化剂,添加Na、Cs、Ca、Cu、Zn、Fe、Ce等碱金属、碱土金属组分,可将低碳烃中无机氯一并脱除,可将无机氯脱至0.1ppm以下,有效提高脱氯效率,降低出口总氯至0.2ppm以下。
具体实施方式
实施例1
(1)将活性氧化铝10g、ZSM-5分子筛65g、椰壳活性炭15g、镁铝水滑石10g混合均匀后磨成粒径小于1000目的微粒;
(2)在步骤(1)所得的混合物微粒中加入适量的田菁粉和水、氢氧化钠溶液,混合后捏合、挤条成型,直径为3-5mm,经120℃干燥4h,再经500℃焙烧4h,得到脱有机氯催化剂TL-1。
(3)将制备的有机氯脱除剂进行堆积比重、测压强度、吸水率、X射线荧光光谱、物理吸附、X射线衍射等物性分析,测试制备的脱有机氯催化剂的物性指标。物性数据见表1。再置于固定床微反评价装置中,进行脱有机氯催化剂微反评价实验。微反评价数据见表2。
实施例2
(1)将活性氧化铝5g、ZSM-5分子筛75g、椰壳活性炭10g、镁铝水滑石10g混合均匀后磨成粒径小于1000目的微粒;
(2)在步骤(1)所得的混合物微粒中加入适量的羧甲基纤维素和3%的稀硝酸、硝酸铯、硝酸铜溶液,混合后捏合、挤条成型,直径为3-5mm,经120℃干燥2h,再经500℃焙烧4h,得到脱有机氯催化剂TL-2。
(3)将制备的有机氯脱除剂进行堆积比重、测压强度、吸水率、X射线荧光光谱、物理吸附、X射线衍射等物性分析,测试制备的脱有机氯催化剂的物性指标。物性数据见表1。再置于固定床微反评价装置中,进行脱有机氯催化剂微反评价实验。微反评价数据见表2。
(4)脱有机氯催化剂TL-2再生:在空气气氛条件下,控制温度为300℃,常压下通空气,空速为1000h-1,再生时间为8h。再置于固定床微反评价装置中,进行脱有机氯催化剂微反评价实验。再生剂微反评价数据见表2。
实施例3
(1)将活性氧化铝30g、ZSM-35分子筛45g、椰壳活性炭20g、镁铝水滑石5g混合均匀后磨成粒径小于1000目的微粒;
(2)在步骤(1)所得的混合物微粒中加入适量的羧甲基纤维素和3%的稀硝酸和硝酸铈溶液,混合后捏合、挤条成型,直径为3-5mm,经120℃干燥2h,再经500℃焙烧2h,得到脱有机氯催化剂TL-3。
(3)将制备的有机氯脱除剂进行堆积比重、测压强度、吸水率、X射线荧光光谱、物理吸附、X射线衍射等物性分析,测试制备的脱有机氯催化剂的物性指标。物性数据见表1。再置于固定床微反评价装置中,进行脱有机氯催化剂微反评价实验。微反评价数据见表2。
表1脱有机氯催化剂物性数据表
表2脱有机氯催化剂微反评价数据表
Claims (6)
1.一种脱有机氯催化剂,其特征在于,以催化剂总质量计,包括质量百分含量的下列组分:5%-30%活性氧化铝,5%-20%活性炭,5%-15%水滑石,35%-75%分子筛;所述的催化剂还包括0.1%~10%催化助剂Ce。
2.根据权利要求1所述的脱有机氯催化剂,其特征在于,所述的脱有机氯催化剂的孔容为0.2 -1.5cm3/g、比表面积为200 -800m2/g。
3.根据权利要求2所述的脱有机氯催化剂,其特征在于,所述的脱有机氯催化剂的孔容为0.5 -1.0cm3/g、比表面积为250 -600m2/g。
4.一种权利要求1所述的脱有机氯催化剂的制备方法,其特征在于,包括:
将活性氧化铝、活性炭、水滑石、分子筛混合均匀后磨成混合物微粒,然后将混合物微粒加入粘结剂、催化助剂盐溶液混合、成型,再经干燥、焙烧后制得。
5.一种权利要求1~3任一项所述的脱有机氯催化剂在对化工原料净化脱除有机氯杂质中的应用,其特征在于,脱除处理后,有机氯含量为0.1ppm以下。
6.根据权利要求5所述的应用,其特征在于,所述的脱有机氯催化剂吸附饱和后再生次数为1~8次,且再生后催化剂的有机氯氯容恢复至原来的99%。
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