CN113600203B - 一种用于合成氯乙烯的钼酸铜催化剂及其制备方法 - Google Patents
一种用于合成氯乙烯的钼酸铜催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 18
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 8
- 238000007038 hydrochlorination reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
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- 239000011684 sodium molybdate Substances 0.000 claims description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
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- 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 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052753 mercury Inorganic materials 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 5
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 5
- 239000005997 Calcium carbide Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- 229910052788 barium Inorganic materials 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
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- 230000008021 deposition Effects 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 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
- B01J23/70—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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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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- 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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Abstract
本发明公开了一种用于合成氯乙烯的钼酸铜催化剂及其制备方法，特别是一种适用于乙炔氢氯化反应合成氯乙烯的非汞催化剂，该催化剂采用主活性组分是为钼酸铜，以钡、镍、钴、铈、锡的化合物的一种及以上为辅活性组分，载体为活性炭，经过浸渍干燥后制得所述催化剂。该催化剂解决了电石乙炔法聚氯乙烯生产中汞催化剂对环境污染的问题，而且具有较好的综合性能，该催化剂活性高、选择性好、绿色环保等优点。
Description
技术领域
本发明涉及一种乙炔氢氯化合成氯乙烯的催化剂领域，尤其是一种用于合成氯乙烯的钼酸铜催化剂及其制备方法。
背景技术
氯乙烯单体是聚氯乙烯重要的合成原料，聚氯乙烯是我国消费和产量最大的合成树脂之一，而我国多煤少油的基本国情决定了乙炔氢氯化法生产氯乙烯仍然在我国占有主导的地位。乙炔氢氯化法合成氯乙烯现在所面临的主要问题之一是汞触媒的使用所带来的环境污染以及汞资源的大量消耗。随着人们环保意识的日益增强和国际限汞条约谈判的日益紧张，无汞触媒的开发在近十年成为电石法聚氯乙烯行业的研究热点之一。
目前无汞催化剂的研究主要集中在非贵金属与贵金属无汞催化剂的研究开发。贵金属无汞催化剂的研究开发近十年来进入鼎盛时期，清华大学、南开大学、华东理工大学、新疆天业等很多研发单位和企业都对贵金属无汞催化剂的开发做了很多工作，使得贵金属无汞催化剂的开发也取得了很大的研究进展。贵金属无汞催化剂虽然转化率高，但是其一次性投入大，反应热点高，热点集中等问题限制了贵金属无汞催化剂的推广应用，贵金属无汞催化剂存在的这些问题使得价格低廉的非贵金属无汞催化剂越来越受人们的关注。
非贵金属催化剂的研发近期也取得了一定的进展，例如CN101497046、CN101671293、CN102151581A分别以Cu、Bi、MoP等非贵金属为主活性组分的催化体系；CN201710174566.X公开了贱金属盐和酰胺类溶剂协同作用的铜基催化剂；CN201910933364.8公开了一种三价铜催化剂及其制备方法在乙炔氢氯化中的应用。本发明中提出的催化剂的活性中心、组成结构、制备方法等明显不同于以上公开的技术内容。
乙炔氢氯化气固相法催化剂的开发和催化剂的活性中心、组成、结构、助剂、载体及载体改性等相辅相成，缺一不可。目前非贵金属催化剂的综合性能并不理想，催化剂还存在寿命短、活性低、容易积炭，容易流失等等问题。
发明内容
针对以上电石法乙炔氢氯化汞催化剂对环境造成污染的问题，非贵金属催化剂的综合性能并不理想，催化剂还存在寿命短、活性低、容易积炭，容易流失等等问题，本发明提供一种用于合成氯乙烯的钼酸铜催化剂及其制备方法，该催化剂活性高，稳定性好，是一种新型无汞催化剂。
如上所述的催化剂包括主活性组分钼酸铜，辅活性组分钡、镍、钴、铈、锡的化合物的一种或任意几种的混合物，载体活性炭、二氧化硅、分子筛的一种或任意几种。
如上所述的催化剂的辅活性组分为氯化钡、硝酸钡、硝酸锌氯化镍、硝酸镍、氯化钴、硝酸钴、氯化铈、硝酸铈、氯化亚锡、四氯化锡的一种或任意几种化合物。
如上所述的催化剂的载体为活性炭、二氧化硅、分子筛的一种或任意几种。
如上所述的一种用于合成氯乙烯的钼酸铜催化剂的制备方法，向氯化铜溶液中加入一定量的钼酸钠和一定量的甘氨酸，在30~100℃水浴中搅拌0.5~3h后，加入一定量的活性炭形成混合溶液，将混合溶液转移至水热反应器中，在80~250℃下反应0.5~3h，45-55℃下烘培8-24h，120-130℃下烘培8-48h，制得钼酸铜催化剂。
如上所述的一种用于合成氯乙烯的钼酸铜催化剂的制备方法应用于乙炔氢氯化铜基催化剂的制备。
本发明提供的一种用于合成氯乙烯的钼酸铜催化剂及其制备方法，在10~180h-1的空速反应时，初始转化率能达到40~99%，氯乙烯的选择性可达到98%以上，解决电石乙炔法聚氯乙烯生产中使用高毒性的汞催化剂，生产中汞消耗量大，对环境污染严重，解决了现有非贵金属催化剂活性低、稳定性较差等问题。
具体实施方式
为了更好的说明本发明，举出以下实例。但本发明的范围并不仅局限于实例，其要求保护的范围记载于权利要求的权项中。
实施例1
将4~8g氯化铜加入到50~100mL水中配制成溶液，再向该溶液中加入6~8g钼酸钠和1~2g甘氨酸，60~70℃水浴中搅拌10～50分钟，继续搅拌5~10分钟后，将溶液转移至水热反应器中，180~260℃下，反应5~10h，过滤得到固体，用蒸馏水洗涤3~5遍，80℃烘干，即得到一种钼酸铜光催化剂。
称量氯化铜0.4g、氯化镍0.4g于烧杯中，随后加入20ml去离子水稀释。再向该溶液中加入0.6g钼酸钠和0.1g甘氨酸，60℃水浴中搅拌30分钟，加入10g活性炭载体，搅拌均匀，常温浸渍24h，然后50℃条件下干燥8h，在125℃条件下干燥24h自然降温后为所制备催化剂样品。
实施例2
称量氯化铜2g、氯化亚锡2g于烧杯中，随后加入20ml去离子水稀释。再向该溶液中加入3.5g钼酸钠和1.2g甘氨酸，80℃水浴中搅拌60分钟，加入10g活性炭载体，搅拌均匀，转移至水热反应器中，120℃下，反应5h，然后50℃条件下干燥8h，在125℃条件下干燥24h自然降温后为所制备催化剂样品。
实施例3
称量氯化铜4g、氯化钴1g于烧杯中，随后加入20ml去离子水稀释。再向该溶液中加入6g钼酸钠和2g甘氨酸，70℃水浴中搅拌120分钟，加入10g活性炭载体，搅拌均匀，转移至水热反应器中，180℃下，反应3h，然后50℃条件下干燥8h，在125℃条件下干燥24h自然降温后为所制备催化剂样品。
实施例4
称量氯化铜6g、硝酸铈1g于烧杯中，随后加入20ml去离子水稀释。再向该溶液中加入7g钼酸钠和1.5g甘氨酸，60℃水浴中搅拌30分钟，加入10g活性炭载体，搅拌均匀，转移至水热反应器中，200℃下，反应3h，然后50℃条件下干燥8h，在125℃条件下干燥24h自然降温后为所制备催化剂样品。
实施例5
称量氯化铜8g、硝酸镍3g于烧杯中，随后加入20ml去离子水稀释。再向该溶液中加入6g钼酸钠和1.5g甘氨酸，60℃水浴中搅拌30分钟，加入10g活性炭载体，搅拌均匀，转移至水热反应器中，230℃下，反应3h，然后50℃条件下干燥8h，在125℃条件下干燥24h自然降温后为所制备催化剂样品。
Claims (3)
1.一种用于合成氯乙烯的钼酸铜催化剂，其特征在于，该催化剂包括主活性组分钼酸铜，辅活性组分为氯化钡、硝酸钡、硝酸锌、氯化镍、硝酸镍、氯化钴、硝酸钴、氯化铈、硝酸铈、氯化亚锡、四氯化锡的一种或任意几种化合物，载体为活性炭、二氧化硅、分子筛的一种或任意几种；
催化剂的制备方法为：向氯化铜、辅助活性组分的混合溶液中加入一定量的钼酸钠和一定量的甘氨酸，在30~100℃水浴中搅拌0.5~3h后，加入一定量的载体形成混合溶液，将混合溶液转移至水热反应器中，在80~250℃下反应0.5~3h，45-55℃下干燥8-24h，120-130℃下干燥8-48h，制得钼酸铜催化剂。
2.根据权利要求1所述的一种用于合成氯乙烯的钼酸铜催化剂的制备方法，其特征，在于向氯化铜、辅助活性组分的混合溶液中加入一定量的钼酸钠和一定量的甘氨酸，在30~100℃水浴中搅拌0.5~3h后，加入一定量的活性炭形成混合溶液，将混合溶液转移至水热反应器中，在80~250℃下反应0.5~3h，45-55℃下干燥8-24h，120-130℃下干燥8-48h，制得钼酸铜催化剂。
3.根据权利要求1所述用于合成氯乙烯的钼酸铜催化剂或权利要求2所述的用于合成氯乙烯的钼酸铜催化剂的制备方法制备的催化剂的应用，其特征在于，应用于乙炔氢氯化合成氯乙烯。
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