CN101896269B - 催化剂再生方法 - Google Patents
催化剂再生方法 Download PDFInfo
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- CN101896269B CN101896269B CN2008801203735A CN200880120373A CN101896269B CN 101896269 B CN101896269 B CN 101896269B CN 2008801203735 A CN2008801203735 A CN 2008801203735A CN 200880120373 A CN200880120373 A CN 200880120373A CN 101896269 B CN101896269 B CN 101896269B
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- extractant
- catalyst
- assorted many
- wolframic acids
- many wolframic
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 238000011084 recovery Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000002253 acid Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 6
- 150000007513 acids Chemical class 0.000 claims description 56
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000571 coke Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229960004132 diethyl ether Drugs 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
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- 238000000926 separation method Methods 0.000 claims description 2
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- 238000005406 washing Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 10
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- 239000010937 tungsten Substances 0.000 abstract description 9
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- 235000019441 ethanol Nutrition 0.000 description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- 150000003839 salts Chemical class 0.000 description 9
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- 239000003377 acid catalyst Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 6
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 3
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
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- 229910052748 manganese Inorganic materials 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
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- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
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- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- 238000004438 BET method Methods 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
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Classifications
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
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Abstract
一种从包括被担载的杂多钨酸的废弃的催化剂中再生钨的方法，其特征在于该方法包括：(a)使废弃的催化剂与萃取剂接触达足以从中萃取至少部分杂多钨酸的时间，所述萃取剂选自水、甲醇、乙醇或任何其两种或更多种的混合物；(b)分离含杂多钨酸的萃取剂和经处理的废弃的催化剂；(c)使含杂多钨酸的萃取剂与强酸离子交换树脂接触而除去其中所含的腐蚀金属，和(d)再生经处理的含杂多钨酸的萃取剂以备随后使用。
Description
本发明涉及一种从用于各种工业规模用途的催化剂中再生杂多酸的方法。特别地，本发明涉及从其中杂多酸担载在支撑体或载体上的废弃的工业催化剂中再生含钨的杂多酸。
杂多酸被广泛用于化学工业中来催化各种需要强酸存在的工业过程。实例包括链烷烃的异构(美国临时专利申请2002/0023859)、制备N-乙酰氨基苯酚(美国专利5387702)、制备双酚、生产乙苯或异丙基苯和醇和烷氧基烷烃(alkoyalkanes)的脱水以生产烯烃。
在诸如这些的方法中，催化剂不可避免地具有有限寿命，其后，它们变成废弃的。换言之，使用它们不再是在技术上或经济上可行的。这样的催化剂随时间变成废弃的一个共同的原因是在催化剂的表面上或者在其孔隙内(如果载体本身是多孔的)有机降解产物(通常称为“焦炭”)的沉积。所述结焦的问题可能本身以各种不希望的方式显现，包括降低的活性(即在给定温度下的进料转化率)和降低的产物选择性(即不希望的副产物的形成提高)。例如，当二氧化硅担载的硅钨酸催化剂用于进行乙醇或乙氧基乙烷的脱水时，随时间渐进的结焦导致副产物乙烷的增加，付出了期望的乙烯的代价。
随时间被担载的杂多酸失去其有效性的第二个原因在于金属在其表面上和在其孔隙中的堆积。由存在于原料中的杂质和缓慢腐蚀其中进行该方法的设备而产生的这些金属通常以小的、但仍然显著的量存在。例如，在通过上述方法生产乙烯中，钴、铬、镍；和铁的堆积可能最终导致大量形成副产物乙烷。
一旦被担载的杂多酸催化剂是废弃的，由于经济原因期望的是从载体中回收杂多酸。由于钨和钨化合物的高价格，对于包括杂多钨酸的催化剂来说，情况特别是如此。本申请中公开的方法因此允许从废弃的催化剂中有效的再生杂多钨酸，由此避免了与由新的钨源形成新鲜催化剂有关的时间和成本。
美国专利5716895公开了再生杂多钼(酸)催化剂的方法，包括将其溶解在水介质中，用过氧化氢氧化溶液，和用无机离子交换材料例如结晶锑酸处理产物。然而，该参考文献中公开的催化剂被用于完全不同的目的，异丁烯醛(methacrolein)和的反应不包含钨。另外，使用锑酸引起了不希望的环境问题以及产生了最终催化剂的潜在污染。WO 2007/003899公开了我们的催化剂所用于的方法。WO2005/107945公开了一种使用阳离子交换树脂从含贵金属的溶液中回收腐蚀金属的方法。US 2968527公开了从水介质中回收钨酸，使用了阴离子交换树脂，随后用氯离子洗脱。JP 56163755公开一种从废弃的催化剂中再生钼磷酸(molybdophosphoric acids)的方法，包括水溶液萃取和在含氧气氛中的热处理。
根据本发明，提供了一种从包括被担载的杂多钨酸的废弃的催化剂中再生杂多钨酸的方法，其特征在于该方法包括：
(a)使废弃的催化剂与萃取剂接触达足以从中萃取至少部分杂多钨酸的时间，所述萃取剂选自水、甲醇、乙醇或任何其两种或更多种的混合物；
(b)分离含杂多钨酸的萃取剂和经处理的废弃的催化剂；
(c)使含杂多钨酸的萃取剂与强酸离子交换树脂接触而除去其中所含的腐蚀金属，和
(d)再生经处理的含杂多钨酸的萃取剂以备随后使用。
已经发现，由通过以上方法再生的杂多钨酸产生的新鲜催化剂具有与等量的由完全新且独立的杂多钨酸源产生的催化剂相同的性能特性。本发明方法因此最小化了购买和使用除最低量的额外的钨或钨化合物以外的任何事物的需要。此外，通过基本上循环先前使用的钨，所述方法产生了重要的环保效益。
在本发明的优选实施方案中，在步骤(a)前，废弃的催化剂用有机液体洗涤，以便除去在其上存在的任何“软”焦炭(容易可溶解的有机材料)。通过这样做，便于在步骤(a)中除去杂多钨酸。尽管有机液体可以是任何有机化合物，但是通常优选使用通常可得的溶剂如C4-C12烷烃(优选地C6-C10烷烃)或其混合物或者液体芳族化合物如甲苯或一种或多种二甲苯。或者存在于焦炭中的更挥发性的有机物中的一些可以在萃取前从废弃的催化剂中通过在除去前在反应器中对其用热氮气、蒸汽或其混合物进行原位处理而被清除。
在本发明方法的步骤(a)中，废弃的催化剂用选自水、甲醇、乙醇或任何其两种或更多种的混合物的萃取剂处理。处理可以通过在填料塔中使废弃的催化剂与萃取剂的连续物流接触来进行。或者，在搅拌下萃取剂和废弃的催化剂可以被密切混合在一起而形成其中发生萃取的浆液。步骤(a)可以在室温下进行，但是优选地通过在提高的温度下，适当地在30-100℃、优选地40-85℃，进行而促进该方法。
萃取剂和废弃的催化剂在一起接触直到发现在接触的条件下没有进一步的杂多钨酸可以被除去。对于给定的温度，通过定期取出混合物样品，分离萃取剂和使用常规定量分析技术测量其中的钨浓度，这可以容易地被确定。
在所公开的萃取剂中，水通常是优选的，因为其从废弃的催化剂中除去更多杂多钨酸的能力以及其的不燃性。相比于乙醇，使用水是有利的，因为它没有溶解焦炭。然而，使用乙醇允许除去孔隙堵塞焦炭并且可以因此提高杂多钨酸的再生。为此，可能有利的是使用乙醇和水的混合物，当处理大量的催化剂时。
在本发明方法的步骤(b)中，使用用于大规模分离液体和固体的由本领域技术人员实施的任何方法，从经处理的废弃的催化剂中分离含杂多钨酸的萃取剂。这通常可以是通过过滤(例如真空过滤、离心过滤)或者在浆液的情况下，通过滗析。如果分离后的萃取剂包含显著量的有机材料，可能必需使用不与萃取剂溶混的上述类型的烷烃通过液液萃取将其除去。添加水可用于促进分离。
含步骤(b)中产生的杂多钨酸的萃取剂将通常包含显著量的腐蚀金属，其已经在上述步骤(a)中从废弃的催化剂中浸析出来。一般地，这些腐蚀金属是过渡金属，特别地镍、钴、铬和铁，即钢的典型组分。重要的是，如果由本文中所述的方法用这些材料制备的催化剂将显示出最佳性能特性的话，在杂多钨酸被再次使用前，这些金属的含量被显著地降低。
如果杂多钨酸将用于制造用于乙醇或乙氧基乙烷脱水成乙烯的催化剂的话，那么重要的是总腐蚀金属与杂多钨酸的摩尔比小于0.25-1。为避免混淆，当计算分子量时，杂多钨酸被假定为完全水合的。对于各种腐蚀金属来说，还优选的是单独的摩尔比如下：铬小于0.22-1；铁，小于0.15-1；镍小于0.1-1和钴小于0.8-1。优选地，总腐蚀金属与杂多钨酸的摩尔比小于0.15-1，最优选地小于0.1-1。在所述方法的步骤(c)中除去腐蚀金属，其包括使含杂多钨酸的萃取剂与强酸离子交换树脂接触。这可以通过使含杂多钨酸的萃取剂与强酸阳离子交换树脂接触来进行。这样的树脂的典型实例是由Rohn and Haas制造的
树脂，例如Amberlyst15H或Amberlyst35H树脂。还可以使用规格类似于这些树脂并且由其它制造商制造的树脂，例如
C145H。以类似于步骤(a)的方式，在固定床中或者在浆液中在室温至100℃的温度下可以进行步骤(c)。对于水萃取剂来说，在大气压力下，优选的温度是大于60℃并且小于90℃。对于乙醇萃取剂来说，在大气压力下，优选的温度是小于60℃。可能有利的是在压力下进行此过程，特别地当来自固定床的钨将被再生时或者如果挥发性溶剂将被使用时。在给定温度和条件下随时间除去腐蚀金属的进程可以继之以取样和定量分析以便确定离子交换的最佳接触时间，使得满足上述低残留水平。
来自步骤(c)的含杂多钨酸的萃取剂可以在步骤(d)中直接使用来制造新鲜催化剂(例如通过使溶液与新鲜的载体接触)。或者，如果这种产物太稀的话，其可以首先通过部分除去萃取剂来浓缩并且如果期望的话可以除去全部的萃取剂以产生固体杂多钨酸。
如本文中使用的术语杂多钨酸包括游离的酸本身和其可溶盐。所述盐尤其包括；杂多钨酸的碱金属、碱土金属、铵(作为反离子)和/或过渡金属盐(其中所述盐可以是全盐(full salt)或分盐(partial salt))。在本发明中所称的杂多钨酸是络合的(complex)、高分子量阴离子，包括氧-连接的金属原子。
一般地，每个阴离子包括12-18个氧-连接的钨原子。这些原子以对称的方式围绕一个或多个中心原子。中心原子优选地是硅或磷，但是可以备选地包括元素周期表中I-VIII族的大量原子中的任一种。这些包括铜、铍、锌、钴、镍、硼、铝、镓、铁、铈、砷、锑、铋、铬、铑、硅、锗、锡、钛、锆、钒、硫、碲、锰镍、铂、钍、铪、铈、砷、钒、锑离子、碲和碘。合适的杂多钨酸包括Keggin、Wells-Dawson和Anderson-Evans-Perloff杂多钨酸。合适的杂多钨酸的具体的实例如下：
18-钨磷酸 - H6[P2W18O62].xH2O
12-钨磷酸 - H3[PW12O40].xH2O
12-钨硅酸 - H4[SiW12O40].xH2O
钨硅酸氢锂 - Li3H[SiW12O40].xH2O
和以下杂多钨酸的游离酸或分盐：
钨磷酸单钾 - KH5[P2W18O62].xH2O
12-钨硅酸单钠 - NaK3[SiW12O40].xH2O
钨磷酸钾 - K6[P2W18O62].xH2O
另外，不同的杂多钨酸和盐的混合物可以存在于废弃的催化剂中。在这方面本发明所描述的优选的是任何基于Keggin或Wells-Dawson结构的那些；更优选地，用于本发明所述方法的所选的杂多钨酸是钨硅酸，或钨磷酸。最优选地，杂多钨酸将是12-钨硅酸(H4[SiW12O40].xH2O)。
优选地，所用的杂多钨酸将具有大于700且小于8500的分子量，优选地大于2800且小于6000。这样的杂多钨酸也包括二聚络合物。
合适的催化剂载体可以是但不限于蒙脱土、粘土、膨润土、硅藻土(diatomous earth)、二氧化钛、活性碳、氧化铝、二氧化硅-氧化铝、二氧化硅-二氧化钛共凝胶、二氧化硅-氧化锆共凝胶、碳涂布的氧化铝、沸石(例如丝光沸石)、氧化锌、火焰裂解氧化物。载体可以是混合氧化物，中性或弱碱性氧化物。二氧化硅载体是优选的，如硅胶载体和通过SiCl4的火焰水解反应产生的载体。优选的载体基本上没有可能不利地影响体系的催化活性的外来的金属或元素。因此，合适的二氧化硅载体为至少99％w/w纯的。杂质总计小于1％w/w，优选地小于0.60％w/w和最优选地小于0.30％w/w。载体的孔隙体积优选地大于0.50ml/g和优选地大于0.8ml/g。
合适的二氧化硅载体包括但不局限于以下中的任一种：GraceDavison
Grade 57，Grace Davison
1252，GraceDavison
SI 1254，Fuji Silysia
Q15，Fuji Silysia
Q10，Degussa
3045和Degussa
3043。
载体颗粒的平均直径是2-10mm，优选地3-6mm。然而，这些颗粒可以是更小的，例如有时候0.5-2mm。
载体的平均孔径(在用杂多钨酸浸渍前)将通常是10-
优选地30-
更优选地50-
和最优选地60-
BET表面积将通常是50-600m2/g和最优选地150-400m2/g。载体将通常具有如下的平均单颗粒压碎强度：至少1kg力，适当地至少2kg力，优选地至少6kg力并且更优选地至少7kg力。载体的堆积密度将通常为至少380g/l，优选地至少395g/l。
单颗粒压碎强度将是通过使用Mecmesin测力计测定的，后者测量了在平行板之间压碎颗粒所需要的最小的力。压碎强度基于对一组至少25个催化剂颗粒测定的平均值。
BET表面积，孔隙体积，孔径分布和平均孔径将由使用Micromeritics TRISTAR 3000静态体积吸附分析器在77K测定的氮气吸附等温线确定。所使用的程序将是应用英国标准方法BS4359：第1部分：1984‘Recommendations for gas adsorption(BET)methods(关于气体吸附(BET)方法的推荐)’和BS7591：第2部分：1992，‘Porosity andpore size distribution of materials(材料的孔隙度和孔径分布)’-Methodof evaluation by gas adsorption(通过气体吸附的评估方法)。应当分别使用BET法(压力范围为0.05-0.20P/Po)和Barrett，Joyner&Halenda(BJH)法(对于孔径20-
)筒化所得的数据，从而得到表面积和孔径分布。
上述数据筒化方法的合适的参考文献是Brunauer，S，Emmett，P H，&Teller，E，J.Amer.Chem.Soc.60，309，(1938)和Barrett，E P，Joyner，LG&Halenda P P，J.Am Chem.Soc.，1951 73 373-380。
适于通过本发明方法处理的优选的杂多钨酸担载的催化剂是具有以下性能的催化剂：
PV＞0.6-0.3x[HPA负载量/催化剂的表面积]
其中PV是干燥的担载的杂多钨酸催化剂的孔隙体积(按ml/g催化剂计)；HPA负载量是存在于干燥的担载的杂多钨酸催化剂中的杂多酸的量(按微摩尔/克的催化剂计)和催化剂的表面积是干燥的担载的杂多钨酸催化剂的表面积(按m2/克的催化剂计)。
浸渍到载体上的杂多钨酸的量将适当地是10wt％-80wt％，优选地20wt％-50wt％，基于杂多钨酸和载体的总重量。
可以使用干燥后的(on drying)催化剂的重量和所使用的载体的重量来通过从前者扣除后者而获得在载体上的酸的重量，这给出了催化剂负载量，作为′g杂多钨酸/kg催化剂′术语。就′克杂多钨酸/升载体′而言的催化剂负载量还可以通过使用已知的或测量的载体的堆积密度来计算。杂多钨酸的优选的催化负载量将是150-600g杂多钨酸/kg催化剂，平均杂多钨酸负载量/干燥的担载的杂多钨酸催化剂的表面积将是大于0.1微摩尔/m2。在所述杂多钨酸担载的催化剂中/上存在的氯化物的量将是小于40ppm，优选地小于25ppm和最优选地小于20ppm。
本发明方法，虽然在工业规模上适用于各种各样的废弃的杂多钨酸催化剂，并且特别地适用于处理用于醇和烷氧基烷烃转化为烯烃，特别地乙醇、乙氧基乙烷和其混合物(含水的)转化为乙烯中的废弃的催化剂。
参考以下实施例，现在举例说明本发明。
实施例1
45g(73ml)的废弃的二氧化硅担载的硅钨酸催化剂(＜4mm直径)置于固定床反应器中。然后，在0.5hr-1的LHSV下，使连续流动蒸馏水(在80℃)通过固定床达6小时并且收集基本上无色的流出物(eluent)。该流出物(effluent)的分析表明大约70％的硅钨酸被再生。然后在相同温度使流出物(eluent)通过Amberlyst 15H离子交换树脂的固定床而除去任何腐蚀金属并且再次收集流出物(effluent)。使用旋转蒸发器(在70℃和小于0.1MPa压力)，从该流出物(eluent)中再生基本上纯的固体硅钨酸，随后是在烘箱中在100℃的随后干燥。
一般地，来自上述第一阶段洗涤的流出物(eluent)包含11ppm铁，2ppm铬，4ppm镍和每一个＜2ppm的钼、锰和铜。在用离子交换树脂处理后，流出物(eluent)的腐蚀金属含量是3ppm铁和＜2ppm铬、镍、钼、锰和铜。
实施例2和3
与实施例1等价的实验，其中在20℃(实施例2)和50℃(实施例3)进行催化剂洗涤，分别实现大约60和65％的硅钨酸的再生。
实施例4
重复实施例1，区别在于45g(73ml)的废弃的二氧化硅担载的硅钨酸(＜4mm直径)被放入固定床反应器中并且使在0.5hr-1的LHSV下的连续流动的无水乙醇在20℃通过所述床达6小时并且收集流出物(eluent)。该流出物(eluent)的分析表明大约60％的硅钨酸被再生。流出物(eluent)是深绿/褐色的，表示存在溶解的有机物。该有机物源自于废弃的催化剂上的焦炭。
实施例5-21
如下表所详述，进行其它的实验。
| 实施例 | 溶剂 | 废弃的催化剂粒径(mm) | 催化剂重量(g) | 催化剂体积(mls) | 温度(℃) | LHSV(ml溶剂/ml催化剂/h-1) | 总萃取时间(hr) | 再生的钨(％) |
| 实施例1 | 水 | ＜4 | 45 | 73 | 80 | 0.5 | 6 | 73 |
| 实施例2 | 水 | ＜4 | 45 | 73 | 20 | 0.5 | 6 | 61 |
| 实施例3 | 水 | ＜4 | 45 | 73 | 50 | 0.5 | 6 | 65 |
| 实施例4 | 乙醇 | ＜4 | 45 | 73 | 20 | 0.5 | 6 | 58 |
| 实施例5 | 乙醇 | ＜4 | 20 | 38 | 20 | 2 | 6 | 59 |
| 实施例6 | 乙醇 | ＜4 | 20 | 38 | 20 | 5 | 6 | 50 |
| 实施例7 | 乙醇 | ＜4 | 20 | 38 | 20 | 8 | 6 | 44 |
| 实施例8 | 乙醇 | ＜4 | 20 | 38 | 20 | 10 | 6 | 35 |
| 实施例9 | 乙醇 | ＜4 | 20 | 38 | 40 | 2 | 6 | 34 |
| 实施例10 | 乙醇 | ＜4 | 20 | 38 | 40 | 5 | 6 | 41 |
| 实施例11 | 乙醇 | ＜4 | 20 | 38 | 40 | 8 | 6 | 32 |
| 实施例12 | 乙醇 | ＜4 | 20 | 38 | 40 | 10 | 6 | 32 |
| 实施例13 | 乙醇 | ＜4 | 20 | 38 | 60 | 2 | 6 | 25 |
| 实施例14 | 乙醇 | ＜4 | 20 | 38 | 60 | 5 | 6 | 19 |
| 实施例15 | 乙醇 | ＜4 | 20 | 38 | 60 | 8 | 6 | 13 |
| 实施例16 | 乙醇 | ＜4 | 20 | 38 | 60 | 10 | 6 | 4 |
| 实施例17 | 乙醇 | ＜4 | 20 | 38 | 20 | 0.5 | 6 | 62 |
| 实施例18 | 乙醇 | ＜4 | 20 | 38 | 20 | 0.5 | 6 | 59 |
| 实施例19 | 乙醇 | ＜4 | 20 | 38 | 20 | 0.2 | 6 | 66 |
| 实施例20 | 乙醇 | ＜1 | 20 | 38 | 20 | 0.2 | 6 | 71 |
| 实施例21 | 水 | ＜1 | 45 | 73 | 80 | 0.5 | 6 | 80 |
Claims (10)
1.一种从包括被担载的杂多钨酸的废弃的催化剂中再生杂多钨酸的方法，其特征在于该方法包括：
(a)使废弃的催化剂与萃取剂接触达足以从中萃取至少部分杂多钨酸的时间，所述萃取剂选自水、甲醇、乙醇或任何其两种或更多种的混合物；
(b)分离含杂多钨酸的萃取剂和经处理的废弃的催化剂；
(c)使含杂多钨酸的萃取剂与强酸离子交换树脂接触而除去其中所含的腐蚀金属，和
(d)再生经处理的含杂多钨酸的萃取剂以备随后使用。
2.权利要求1的方法，其特征在于，在步骤(a)前用有机液体洗涤废弃的催化剂而除去软焦炭。
3.权利要求1的方法，其特征在于，在步骤(a)前用热氮气、蒸汽或其混合物处理废弃的催化剂。
4.权利要求1的方法，其特征在于，步骤(a)在40-85℃的温度进行。
5.权利要求1的方法，其特征在于，萃取剂是乙醇和水的混合物。
6.权利要求1的方法，其特征在于，萃取剂是水。
7.权利要求1的方法，其特征在于，萃取剂是乙醇，和步骤(c)之前是其中使用液-液萃取除去溶于萃取剂的软焦炭的步骤。
8.权利要求1的方法，其特征在于，废弃的催化剂已经用于进行乙氧基乙烷、乙醇或其混合物的脱水来形成乙烯。
9.权利要求1的方法，其特征在于，再生的杂多钨酸被再次利用来制造新鲜的担载的杂多钨酸。
10.权利要求2的方法，其特征在于，有机液体是C6-C10烷烃或其混合物。
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| US3644497A (en) * | 1968-11-01 | 1972-02-22 | Celanese Corp | Conversion of ethylenically unsaturated compounds using heteropoly-molybdic and heteropolytungstic acids as catalysts |
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