CN108435193B - 一种可再生的脱除有机氯催化剂及其制备方法 - Google Patents
一种可再生的脱除有机氯催化剂及其制备方法 Download PDFInfo
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- CN108435193B CN108435193B CN201810325562.1A CN201810325562A CN108435193B CN 108435193 B CN108435193 B CN 108435193B CN 201810325562 A CN201810325562 A CN 201810325562A CN 108435193 B CN108435193 B CN 108435193B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 6
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 16
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 150000000703 Cerium Chemical class 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
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- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical group [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
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- 239000003795 chemical substances by application Substances 0.000 description 5
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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 description 5
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- 229910001504 inorganic chloride Inorganic materials 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 3
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- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 3
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- 238000001354 calcination Methods 0.000 description 3
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017970 MgO-SiO2 Inorganic materials 0.000 description 1
- 229910017315 Mo—Cu Inorganic materials 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 1
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
本发明公开了一种可再生的脱除有机氯催化剂及其制备方法。该催化剂以铝源、硅源和镁源合成的复合氧化物为载体，以Ni、Mo、Cu、Ce为活性组分。按催化剂的质量百分比计，其活性组分中NiO含量为6.2‑15.6%，CuO含量为16.1‑25.4%，MoO3含量为1.7‑4.6%，CeO2含量为1.5‑2.5%，其余为载体；该催化剂以复合氧化物为载体，能较好的分散活性金属，具有有序孔道结构，特定孔径，孔容较大。能有效的脱除有机氯，避免后续的装置被无机氯腐蚀，提高油品的品质。同时该催化剂能持续再生，减少开停工时间，降低生产成本。
Description
技术领域
本发明涉及一种可再生的用于脱除含氯石脑油中有机氯化物的催化剂及其制备方法，属于油品精制领域。
背景技术
在油田的开采后期，为了增加油田的产量，会使用一些含有机氯化物的助剂来增加采油率，导致部分原油中氯化物含量较高，含氯化合物主要富集在石脑油。石脑油中的氯化物主要是氯代烷烃，例如：三氯甲烷，二氯甲烷，三氯乙烷等。目前原油的脱盐工艺，只能脱除原油中的无机氯化物，不能脱除其中的有机氯化物。石脑油作为乙烯生产和催化重整的原料，石脑油中有机氯化物对设备不产生腐蚀，但是在进行预加氢过程中，有机氯在高温高压及氢气存在的条件下发生化学反应生产氯化氢，会腐蚀加氢***下游设备。例如：腐蚀预加氢***的空冷设备、水冷设备；氯化氢和加氢产生的氨反应生成氯化铵，堵塞管道；甚至进入预加氢循环氢压缩机的入口，严重影响循环氢压缩机的正常运转。为了防止有机氯在原油加工过程中转化为氯化氢造成设备的腐蚀，许多研究人员开发出多种类型的脱氯剂，有的脱氯剂已经工业应用多年。但是，这些脱氯剂主要集中在对馏分油中无机氯化物的脱除，针对有机氯的脱除的脱氯剂还鲜有报道。US5928500描述了一种脱除烃组分中微量有机氯化物的方法，该方法采用多孔性高比表面积的硅土做载体，Ni，Co或铁及其混合物的金属或金属氧化物为活性组分的吸附剂，将有机氯化物转化为金属氯化物从而将其脱除。CN200810049261专利中描述了一种脱除有机氯化物的吸附剂，这种吸附剂采用多孔性物质，诸如分子筛、氧化铝、活性炭为载体，浸渍金属氯化物或金属氯化物与金属硫酸盐的混合物。该吸附剂能够在含水的条件下将有机氯化物转化为无机氯化物，然后再用水洗的方法去除无机氯化物，这将增加脱氯精制步骤，造成工艺繁琐且还涉及到水洗后进一步脱除水分的问题。浸渍法虽然制备简易，但会造成吸附剂的表面积和孔容下降剧烈，从而影响动态吸附效果与床层寿命。US3864243公开了一种脱除烯烃组分中氯化物和其它杂质的方法，在室温、常压条件下，用孔径8A左右的13X或10X沸石分子筛可以将烃组分中氯化物吸附脱除。US20120190906专利中公开了分子筛的硅铝比对脱除有机氯容量的影响，结果表明硅铝比低于1.25的13X分子筛具有更高的有机氯吸附容量。13X分子筛虽然对有机氯具有一定的脱除效果，但总吸附容量有限且动态吸附速率低，使用寿命短。
发明内容
本发明主要针对石脑油中脱除有机氯的催化剂氯容低、不可再生等不足之处，开发出一种可再生的用于脱除含氯石脑油等油品中有机氯化物的催化剂。本发明提供了一种可再生的脱除有机氯的催化剂及其制备方法。本发明催化剂具有良好脱除有机氯性能，并可再生重复利用。
本发明催化剂是以铝源、硅源和镁源合成的复合氧化物为载体，以Ni、Mo、Cu、Ce为活性组分制得一种可再生的脱除有机氯催化剂。
所述的催化剂，其特征在于：所述的铝源、硅源和镁源合成的复合氧化物，按质量百分比计SiO2含量为3%~10%，MgO含量为9.2~18.9%，其余为Al2O3。
所述催化剂活性组分含量以催化剂总质量计，其活性组分中NiO含量为6.2-15.6%，CuO含量为16.1-25.4%，MoO3含量为1.7-4.6%，CeO2含量为1.5-2.5%。
所述的催化剂，其特征在于：该催化剂的比表面积为430~526m2/g，孔容为0.85~1.1ml/g，孔径为4-10nm。
所述的催化剂的制备方法，其特征在于：将一定量的铝源、硅源、镁源、可溶性的镍盐、表面活性剂和水混合均匀，得到初始溶胶凝胶混合物移入合成釜中密封，在150~220℃晶化8~24小时。将晶体浆液的pH值调节至中性，向反应釜中加入一定量的可溶性的钼盐、可溶性的铜盐和可溶性的铈盐，进行离子交换反应8~28h。待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应。经100~150℃干燥2~4小时，500~700℃焙烧3~6小时后得到一种可再生的脱除有机氯催化剂。
按照本发明提供的催化剂，所述孔体积、比表面积、孔直径采用氮低温吸附法测定。
按照本发明提供的方法制备的一种可再生脱除有机氯催化剂适用于含有机氯的馏分油进行处理，能有效的脱除有机氯，生产含较低氯的馏分油。
本发明的上述技术方案与现有技术相比具有以下优点：
（1）本催化剂从分子结构设计的角度出发，制备出的催化剂具有有序孔道结构，特定孔径，孔容较大。利用催化剂低温吸附有机氯、高温转化脱附有机氯的性能，解决以往催化剂依靠单纯吸附脱除无机氯活性无法吸附有机氯的弊端，同时解决了有机氯吸附类催化剂氯容过低无法再生的问题。
（2）硅酸镁、硅酸铝吸附剂对石脑油中的有机氯化物均有较好的吸附能力，两种物质可看做MgO·SiO2、Al2O3 .SiO2，即负载了金属氧化物的二氧化硅。在混合吸附剂中，氧化镁与氧化铝两种金属氧化物具有协同作用，增加了吸附剂的极性，从而提高了吸附剂对石脑油中氯化物的吸附能力。
（3）Ce利于Ni-Mo-Cu等活性组分在载体表面上更好的分散，抑制晶粒的增长，催化剂的比表面积和孔容增大，氯容增加。在催化剂焙烧的过程中Ce3+氧化变价为Ce4+，而Ce4+具有更强的得电子能力，即L酸量增加，Ce改性催化剂的总酸量增加，能有效的抑制油品烯烃聚合，防止催化剂结焦，提高催化剂的抗结焦能力，延长催化剂的脱氯寿命。
（4）将环境友好型的镍-氨溶液作为模板剂使用，成功的将活性组分镍嵌入微孔催化剂前驱体中，为后续的Ni-Mo-Cu-Ce为活性组分催化剂的合成提供的保证。由于镍嵌入微孔中，在温度升高时能较好的保护镍原子，同时镍将吸附在催化剂上的活性氯激活，通过原子转移作用，让其从催化剂脱附；并且保证催化剂上的镍免于中毒，可再生循环使用。
具体实施实例：
下面结合具体实施案例来详述本发明催化剂的特点、制备方法及其催化性能，但是本发明不仅限于这些例子，也不构成对发明实施范围的任何限定。
实施例1：
将197g铝溶胶（Al2O3的含量22%）、33.3g硅溶胶（SiO2的含量30%）、38.1g硝酸镍、2.5g四乙基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在220℃晶化8小时。用0.5mol/L尿素将晶体浆液的pH值调节至中性，加入4.28g钼酸铵、59.7g硝酸铜和6.3g硝酸铈，进行离子交换反应8h。待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应。经150℃干燥2小时，500℃焙烧6小时后得到可再生吸附脱氯催化剂Cat1。
实施例2：
将179g铝溶胶、10g硅溶胶、44.6g氯化镁、15.1g硝酸镍、2.5g十六烷基三甲基溴化铵和300g水，搅拌10h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在150晶化8小时。用0.5mol/L尿素将晶体浆液的pH值调节至中性，加入6.26g钼酸铵、59.7g硝酸铜和6.3g硝酸铈，进行离子交换反应28h。待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应。经120℃干燥4小时，500℃焙烧6小时后得到可再生吸附脱氯催化剂Cat2。
实施例3
将192.5g铝溶胶、23g硅溶胶、33g氯化镁、26.6g硝酸镍、2.5g四乙基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在220℃晶化20小时。用0.5mol/L尿素将晶体浆液的pH值调节至中性，加入4.28g钼酸铵、48.7g硝酸铜和5.1g硝酸铈，进行离子交换反应20h。待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应。经120℃干燥3小时，600℃焙烧5小时后得到可再生吸附脱氯催化剂Cat3。
实施例4：
将244g铝溶胶、23g硅溶胶、21.7g氯化镁、26.6g硝酸镍、2.5g十六烷基三甲基溴化铵和300g水，搅拌6h，混合均匀，得到初始溶胶凝胶混合物，初始溶胶凝胶物料移入合成釜中密封，在180℃晶化20小时。用0.5mol/L尿素将晶体浆液的pH值调节至中性，加入2.3g钼酸铵、37.8g硝酸铜和3.78g硝酸铈，进行离子交换反应28h。待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应。经100℃干燥4小时，700℃焙烧3小时后得到可再生吸附脱氯催化剂Cat4。
实施例5：
本实施例对上述实施例1～4的脱氯催化剂和现有技术的催化剂Cat5活性对比测定。
对上述产品和焦化汽油脱硅催化剂的孔性质和酸性质进行分析，分析结果如表1
表1 不同催化剂的物化性质
从表1可以看出本发明提供的催化剂Cat2~4载体中引入了MgO，相比未引入MgO的Cat1的具有更优的比表面积和孔容。本发明提供的催化剂Cat1~4通过特定的制备工艺，相比同等组成下的γ-Al2O3具有更大的孔径和孔容。
将各实施例制备的催化剂分别取30ml装入Φ27×3.5mm的反应管，催化剂床层高度48mm，所用原料油为石脑油性质见表2。
表2 石脑油性质
| 项目 | 密度，g/cm<sup>3</sup> | 总氯，μg/g |
| 石脑油 | 0.64 | 246 |
选用分析仪： KY-200微库仑氯含量滴定仪测定油中有机氯。取30ml催化剂装入固定床反应器，进行器内活化，通入氢气，调整***压力为0.7MPa，氢气量为50mL/min，以10℃/min升温至230℃，恒温2h，然后再以相同升温速率升温到400℃，恒温4h使催化剂完全活化。活化结束后，装置置换为氮气，泵入原料油石脑油，进油空速为1.5h-1，反应温度为150℃，反应压力为0.7MPa，氮气/油比100:1进行脱氯实验，脱氯后产品经水洗脱除无机氯后分析有机氯含量。待催化剂的脱氯效果下降后，将催化剂以10℃/min升温至250℃，反应压力提高至1.4 MPa，用氮气进行吹扫，待反应器出口气体检测氯含量为零，停止再生。反应温度降温至150℃，压力降至0.7MPa，重新进行脱氯实验。反应一定时间后取样分析，记录反应结果如表3所示。
表3 脱氯活性测定结果总氯，μg/g
从表3的数据可知，Cat1，Cat2，Cat3，Cat4四种脱氯催化剂在石脑油有机氯含量约240μg/g原料中进行脱除有机氯实验，有机氯脱除达到97.9%以上，而对比催化剂Cat5在有机氯存在的的环境中脱除有机氯效果较差。为了进一步了解本发明催化剂的性能下面对催化剂Cat 3进行再生实验，实验结果见表3。实验结果表明：催化剂Cat3催化剂能有效的吸附脱除有机氯，并且能再生，重复使用。发明人还采用了上述方法对其他各实施例所得的催化剂进行了长周期实验，均能得到较好的结果，表明本发明催化剂具有较好的活性和稳定性。
Claims (7)
1.一种可再生的脱除有机氯催化剂，其特征在于：该催化剂是以铝源、硅源和镁源合成的复合氧化物为载体，以Ni、Mo、Cu、Ce为活性组分，该催化剂的制备方法如下：
将一定量的铝源、硅源、镁源、可溶性的镍盐、表面活性剂和水混合均匀，得到初始溶胶凝胶混合物移入合成釜中密封，在150~220℃晶化8~24小时；将晶体浆液的pH值调节至中性，向反应釜中加入一定量的可溶性的钼盐、可溶性的铜盐和可溶性的铈盐，进行离子交换反应8~28h；待反应结束，将上述浆液加入絮凝剂沉淀、过滤、洗涤、干燥、挤条成型，过滤后液体回用用于下次反应；经100~150℃干燥2~4小时，500~700℃焙烧3~6小时后得到一种可再生的脱除有机氯催化剂；
所述催化剂的制备方法的表面活性剂为四乙基溴化铵或十六烷基三甲基溴化铵。
2.按照权利要求1所述的催化剂，其特征在于：所述的复合氧化物载体，按重量百分比计SiO2含量为3%~10%，MgO含量为9.2~18.9%，其余为Al2O3。
3.按照权利要求1所述的催化剂，其特征在于：所述的铝源为铝溶胶；硅源为硅溶胶；镁源为氯化镁。
4.根据权利要求1所述的催化剂，其特征在于：该催化剂的比表面积为430~526m2/g，孔容为0.85~1.1ml/g，孔径为4-10nm。
5.按照权利要求1中所述的催化剂，其特征在于：催化剂活性组分含量以催化剂总质量计，其活性组分中NiO含量为6.2-15.6%，CuO含量为16.1-25.4%，MoO3含量为1.7-4.6%，CeO2含量为1.5-2.5%。
6.根据权利要求1所述的催化剂，其特征在于：所述催化剂的制备方法用尿素将晶体浆液pH值调至中性。
7.根据权利要求1所述的催化剂，其特征在于：所述催化剂的制备方法的可溶性的钼盐、铜盐及铈盐为其铵盐或硝酸盐。
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| CN103611566A (zh) * | 2013-12-13 | 2014-03-05 | 武汉科林精细化工有限公司 | 一种高含氯油品加氢脱氯催化剂及其制备方法 |
| CN104492480A (zh) * | 2014-12-15 | 2015-04-08 | 武汉科林精细化工有限公司 | 一种用于脱除塑料油中有机氯的催化剂及其制备方法 |
| WO2017083018A1 (en) * | 2015-11-13 | 2017-05-18 | Sabic Global Technologies B.V. | A catalytic process for reducing chloride content of a hydrocarbon feed stream |
| CN105478000A (zh) * | 2015-12-30 | 2016-04-13 | 沈阳三聚凯特催化剂有限公司 | 一种用于净化重整再生气的脱氯剂及其制备方法 |
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