CN102974342B - Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof - Google Patents
Catalyst for preparing cyclohexene from benzene by selective hydrogenation and preparation method thereof Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 102
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims 1
- 239000012153 distilled water Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000000996 additive effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract 2
- 230000009849 deactivation Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910002787 Ru-Ni Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910002793 Ru–Ni Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KFKXDXMQVFMFET-UHFFFAOYSA-N boron ruthenium Chemical compound [Ru].[B] KFKXDXMQVFMFET-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000003375 selectivity assay Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种苯选择性加氢生成环己烯的催化剂及其制备方法，可以应用于苯选择性加氢制备环己烯的工业生产中，具有高活性和环己烯的高选择性，能有效避免苯的深度加氢以及其它副反应，并且反应稳定性良好。 The invention relates to a catalyst for selective hydrogenation of benzene to generate cyclohexene and a preparation method thereof, which can be applied to the industrial production of cyclohexene by selective hydrogenation of benzene, and has high activity and high selectivity of cyclohexene. It can effectively avoid the deep hydrogenation of benzene and other side reactions, and the reaction stability is good.
背景技术 Background technique
环己烯是一种重要的有机合成中间体，具有活泼的双键，作为有机化工原料，可广泛的应用于医药、农药、农用化学品、饲料添加剂、聚酯以及其他精细化学品的生产，尤其环己烯的深加工产物环己酮和己二酸是合成聚酰胺纤维中大量使用的中间体。20世纪80年代以来，国外提出由苯选择性加氢生产环己烯，并成功地实现了工业化。90年代以后，苯选择性加氢制环己烯催化剂的重要性才引起我国大的科研单位、重点高校和石化公司的重视，但研究进展缓慢。开发具有自主知识产权的新型催化体系，缩短我国和发达国家的距离，具有十分重要的意义。 Cyclohexene is an important organic synthesis intermediate with active double bonds. As an organic chemical raw material, it can be widely used in the production of medicines, pesticides, agricultural chemicals, feed additives, polyesters and other fine chemicals. In particular, cyclohexanone and adipic acid, the deep-processing products of cyclohexene, are widely used intermediates in the synthesis of polyamide fibers. Since the 1980s, foreign countries proposed the selective hydrogenation of benzene to produce cyclohexene, and successfully realized industrialization. After the 1990s, the importance of catalysts for the selective hydrogenation of benzene to cyclohexene attracted the attention of large scientific research units, key universities and petrochemical companies in my country, but the research progress was slow. It is of great significance to develop new catalytic systems with independent intellectual property rights and shorten the distance between my country and developed countries.
1972年杜邦公司用RuCl3为催化剂在高压反应釜中进行了苯加氢反应，同时在反应体系中加入水，环己烯收率为32%（DE2221139）。US5589600公开了一种使用共沉淀法制备的Ru-Ni双金属催化剂。最高收率40%。日本旭化成公司使用沉淀法制备的Ru-Zn催化剂（US4734536），环己烯最高收率可达50%，并成功地实现了工业化，其工业指标为：环己烯收率30%，选择性80%。但是由于非负载型催化剂制备方式比较繁琐，贵金属Ru的利用率低，导致催化剂的价格昂贵，并且对硫化物比较敏感，严重影响了催化剂的寿命。同时作为非负载的纳米级颗粒催化剂，存在反应产物和催化剂分离的问题以及严重的催化剂损失问题，所以针对该课题的负载型催化剂研究成为新的热点。 In 1972, DuPont used RuCl3 as a catalyst to carry out benzene hydrogenation reaction in a high-pressure reactor, and added water to the reaction system at the same time, and the yield of cyclohexene was 32% (DE2221139). US5589600 discloses a Ru-Ni bimetallic catalyst prepared by co-precipitation method. The highest yield is 40%. The Ru-Zn catalyst (US4734536) prepared by Japan Asahi Kasei Company by precipitation method has the highest yield of cyclohexene up to 50%, and has successfully realized industrialization. Its industrial indicators are: cyclohexene yield 30%, selectivity 80% %. However, due to the cumbersome preparation method of the unsupported catalyst and the low utilization rate of the precious metal Ru, the catalyst is expensive and sensitive to sulfide, which seriously affects the life of the catalyst. At the same time, as an unsupported nano-particle catalyst, there are problems of separation of reaction products and catalysts and serious catalyst loss, so the research on supported catalysts for this topic has become a new hot spot.
国内方面CN13373786A公开了一种苯选择性加氢制环己烯催化剂及其制造方法，该催化剂由活性组分、助剂、添加剂和分散剂四种组分组成。所述活性组分为Ru、Th、Pa中的一种，助剂为W、Fe、Co、Ni、Zn、Mo或Cd中的一种，添加剂为Na、B、K、Li中的一种，分散剂为氧化锆。所述催化剂的制备方法是将活性组分和助剂前体吸附在分散剂上，再用化学还原剂还原，其使用的还原剂为NaBH4，然后将所得固体洗涤、干燥制得催化剂。 Domestically, CN13373786A discloses a catalyst for the selective hydrogenation of benzene to cyclohexene and its manufacturing method. The catalyst consists of four components: active components, auxiliary agents, additives and dispersants. The active component is one of Ru, Th, Pa, the additive is one of W, Fe, Co, Ni, Zn, Mo or Cd, and the additive is one of Na, B, K, Li , the dispersant is zirconia. The preparation method of the catalyst is as follows: active components and auxiliary agent precursors are adsorbed on the dispersant, and then reduced by a chemical reducing agent, the reducing agent used is NaBH 4 , and then the obtained solid is washed and dried to obtain the catalyst.
CN1446625A公开了一种苯选择性加氢非晶态钌硼催化剂，该催化剂为负载非晶态Ru-B或RuB-M合金的催化剂，所述M为Fe、Co、Ni、Zn或Cr中的一种或几种，载体为氧化锆、氧化硅或氧化铝。该催化剂可提高苯选择性加氢的活性。以上的几种制备催化剂的方式使用了不同的配方组成，获得了较高的环己烯收率。但是，由于苯制环己烯的反应过程主要是传质控制，传质效率直接决定最终收率。因此载体的物化性质对活性组分的分散效果和原料以及产物的传质效果都有重要的作用。 CN1446625A discloses a kind of benzene selective hydrogenation amorphous state ruthenium boron catalyst, and this catalyst is the catalyst of loading amorphous state Ru-B or RuB-M alloy, and described M is Fe, Co, Ni, Zn or Cr One or more, the carrier is zirconia, silicon oxide or aluminum oxide. The catalyst can enhance the activity of selective hydrogenation of benzene. The above several ways of preparing the catalyst use different formulations to obtain a higher yield of cyclohexene. However, since the reaction process of benzene to cyclohexene is mainly controlled by mass transfer, the mass transfer efficiency directly determines the final yield. Therefore, the physical and chemical properties of the carrier play an important role in the dispersion effect of active components and the mass transfer effect of raw materials and products.
发明内容 Contents of the invention
本发明的目的是提供一种新型的具有高活性、高选择性和良好稳定性的苯加氢制环己烯催化剂及其制备方法。该催化剂相比以往催化剂具有更大的比表面积、平均孔径以及孔隙率，因此可以保证苯选择性加氢具有更高的传质效率，能够在同等的活性组分负载量下，达到更好的反应效果。 The object of the present invention is to provide a novel catalyst for preparing cyclohexene from hydrogenation of benzene with high activity, high selectivity and good stability and a preparation method thereof. Compared with previous catalysts, this catalyst has larger specific surface area, average pore size and porosity, so it can ensure that the selective hydrogenation of benzene has higher mass transfer efficiency, and can achieve better under the same active component loading. Reaction effect.
本发明提出的一种苯选择性加氢生成环己烯的催化剂，由活性组分、助剂和分散载体组成，活性组分占1~10wt%，助剂占0.01~2wt%，其余为分散载体，其总重量满足100%；其中：分散载体为ZrO2、SiO2或TiO2中一种以上，活性组分为Ru、Pt或Pa中任一种，助剂为Fe、Co、Ni、Cu、Mn或Zn中任一种。 A catalyst for the selective hydrogenation of benzene to generate cyclohexene proposed by the present invention is composed of active components, auxiliary agents and dispersed carriers, the active components account for 1-10wt%, the auxiliary agents account for 0.01-2wt%, and the rest are dispersed The carrier, the total weight of which satisfies 100%; wherein: the dispersed carrier is more than one of ZrO 2 , SiO 2 or TiO 2 , the active component is any of Ru, Pt or Pa, and the auxiliary agent is Fe, Co, Ni, Any of Cu, Mn or Zn.
本发明提出的一种苯选择性加氢生成环己烯的催化剂的制备方法，具体步骤如下： A kind of preparation method of the catalyst that the selective hydrogenation of benzene that the present invention proposes generates cyclohexene, concrete steps are as follows:
(1)常温下，分散载体的前驱体盐和氨水按照1:1~20的摩尔比混合后反应产生沉淀，得到沉淀氧化物载体，将沉淀过滤，陈化12h后得到凝胶；将凝胶溶解于水中加入过氧化氢，调节溶液pH值为9.0~12.0，在70~99℃温度下，老化回流50h后，将沉淀过滤干燥、并于300~600℃下焙烧2~5h，得到分散载体；氧化物载体与过氧化氢摩尔比为1:0.1~5； (1) At room temperature, the precursor salt of the dispersed carrier and ammonia water are mixed according to the molar ratio of 1:1~20 and then react to produce a precipitate to obtain a precipitated oxide carrier, which is filtered and aged for 12 hours to obtain a gel; Dissolve in water and add hydrogen peroxide to adjust the pH value of the solution to 9.0~12.0. After aging and refluxing for 50 hours at a temperature of 70~99°C, filter and dry the precipitate, and roast at 300~600°C for 2~5 hours to obtain a dispersed carrier ; The molar ratio of oxide carrier to hydrogen peroxide is 1:0.1~5;
(2)将活性组分前驱体盐以及助剂前驱体盐按比例配制成溶液，浸渍于步骤(1)得到的分散载体上，加入氨水调节溶液pH值为10~12，陈化1h后干燥，在400℃下焙烧，在氢气流中180~300℃还原3h，即得到所需催化剂。 (2) Prepare the active component precursor salt and auxiliary agent precursor salt into a solution in proportion, impregnate it on the dispersed carrier obtained in step (1), add ammonia water to adjust the pH value of the solution to 10~12, and dry it after aging for 1 hour , calcined at 400°C, and reduced for 3 hours at 180~300°C in a hydrogen stream to obtain the desired catalyst.
本发明中，所述分散载体的前驱体盐为正硅酸乙酯、ZrO2或TiO2盐酸盐。 In the present invention, the precursor salt of the dispersed carrier is ethyl orthosilicate, ZrO 2 or TiO 2 hydrochloride.
本发明中，活性组分前驱体盐为Ru、Pt或Pd硝酸盐。 In the present invention, the active component precursor salt is Ru, Pt or Pd nitrate.
本发明中，助剂前驱体盐为Fe、Co、Ni、Cu、Mn或Zn硝酸盐。 In the present invention, the auxiliary agent precursor salt is Fe, Co, Ni, Cu, Mn or Zn nitrate.
本发明的催化剂在苯选择性加氢合成环己烯反应中使用条件为：温度100~300℃；氢压力2.0MPa~6.0MPa；苯/蒸馏水介质=0.1~3.0（wt/wt）；硫酸盐添加剂/催化剂=5.0~15.0；苯选择性加氢催化反应具有良好的环己烯收率。 The conditions for the catalyst of the present invention to be used in the selective hydrogenation of benzene to synthesize cyclohexene are: temperature 100-300°C; hydrogen pressure 2.0MPa-6.0MPa; benzene/distilled water medium = 0.1-3.0 (wt/wt); sulfate Additive/catalyst = 5.0~15.0; benzene selective hydrogenation catalytic reaction has good yield of cyclohexene.
与现已报道的催化剂相比，本发明的优点是： Compared with existing reported catalyzers, the advantages of the present invention are:
1、本发明制备的催化剂，活性选择性等综合性能指标达到了工业应用标准。 1. The comprehensive performance indicators such as activity and selectivity of the catalyst prepared by the present invention have reached the industrial application standard.
2、相比与以往的以ZrO2为分散载体的催化剂，本发明制备的催化剂具有更加适合苯选择性加氢反应的孔道结构。 2. Compared with the previous catalyst with ZrO2 as the dispersed carrier, the catalyst prepared by the present invention has a pore structure more suitable for the selective hydrogenation reaction of benzene.
3、沉淀剂使用廉价的氨水，不用价格昂贵的NaOH，催化剂制备成本低。 3. The precipitant uses cheap ammonia water instead of expensive NaOH, and the catalyst preparation cost is low.
4、该方法不需使用价格昂贵的NaBH4作为还原剂，进一步降低了催化剂的综合成本。 4. The method does not need to use expensive NaBH 4 as a reducing agent, further reducing the overall cost of the catalyst.
具体实施方式 Detailed ways
下面通过实施例进一步说明本发明。 The present invention is further illustrated below by way of examples.
实施例1 Example 1
将市售的ZrO2在300℃下焙烧2h后备用。将一定量的RuCl3·xH2O溶于蒸馏水（以金属质量占分散载体质量的8%），等体积真空浸渍后，置于85℃流动空气中干燥24h，并于5ml/min氢气流中在250℃还原3h。得到催化剂A。 Commercially available ZrO2 was calcined at 300 °C for 2 h before use. Dissolve a certain amount of RuCl 3 ·xH 2 O in distilled water (8% of the weight of the dispersed carrier based on the weight of the metal), vacuum impregnate with equal volume, dry it in flowing air at 85°C for 24 hours, and put it in a hydrogen flow of 5ml/min. Reduction at 250°C for 3h. Catalyst A is obtained.
实施例2 Example 2
ZrOCl2·8H2O与NH3·H2O按照1:3的摩尔比制成沉淀，制成凝胶后，按Zr（OH）4与双氧水比例为1:0.2加入，后在96℃、pH=11.5下老化回流50h后，过滤干燥，并在520℃下焙烧1h得到。将一定量的RuCl3·xH2O溶于蒸馏水（以金属质量占分散载体质量的8%），等体积真空浸渍后，置于85℃流动空气中干燥24h，并于5ml/min氢气流中在250℃还原3h。得到催化剂B。 ZrOCl 2 ·8H 2 O and NH 3 ·H 2 O are precipitated at a molar ratio of 1:3. After making a gel, add Zr(OH) 4 and hydrogen peroxide at a ratio of 1:0.2. After aging at pH=11.5 and refluxing for 50h, it was obtained by filtering, drying, and calcining at 520°C for 1h. Dissolve a certain amount of RuCl 3 ·xH 2 O in distilled water (8% of the weight of the dispersed carrier based on the weight of the metal), vacuum impregnate with equal volume, dry it in flowing air at 85°C for 24 hours, and put it in a hydrogen flow of 5ml/min. Reduction at 250°C for 3h. Catalyst B is obtained.
实施例3 Example 3
ZrOCl2·8H2O与NH3·H2O按照1:3制成沉淀，制成凝胶后，按Zr(OH)4与双氧水比例为1:0.2加入，后在96℃、pH=11.5下老化回流50h后，过滤干燥，并在520℃下焙烧1h得到。将一定量的RuCl3·xH2O溶于蒸馏水（以金属质量占分散载体质量的8%），同时按照摩尔比Ru:Fe=1:0.2加入FeCl3后，等体积真空浸渍后，置于85℃流动空气中干燥24h，并于5ml/min氢气流中在250℃还原3h。得到催化剂C。 ZrOCl 2 · 8H 2 O and NH 3 · H 2 O were precipitated at a ratio of 1:3. After making a gel, the ratio of Zr(OH) 4 and hydrogen peroxide was added at a ratio of 1:0.2, and then at 96°C, pH=11.5 After aging at reflux for 50h, filter and dry, and roast at 520°C for 1h. Dissolve a certain amount of RuCl 3 ·xH 2 O in distilled water (8% of the weight of the dispersed carrier based on the weight of the metal), and add FeCl 3 according to the molar ratio Ru:Fe=1:0.2. Dry in flowing air at 85°C for 24h, and reduce at 250°C for 3h in a hydrogen stream of 5ml/min. Catalyst C is obtained.
实施例4 Example 4
ZrOCl2·8H2O与NH3·H2O按照1:3制成沉淀，制成凝胶后，按Zr(OH)4与双氧水比例为1:0.2加入，后在96℃、pH=11.5下老化回流50h后，过滤干燥，并在520℃下焙烧1h得到。将一定量的RuCl3·xH2O溶于蒸馏水（以金属质量占分散载体质量的8%），同时按照摩尔比Ru:Ni=1:0.2加入Ni(NO3)2后，等体积真空浸渍后，置于85℃流动空气中干燥24h，并于5ml/min氢气流中在250℃还原3h。得到催化剂D。 ZrOCl 2 · 8H 2 O and NH 3 · H 2 O were precipitated at a ratio of 1:3. After making a gel, the ratio of Zr(OH) 4 and hydrogen peroxide was added at a ratio of 1:0.2, and then at 96°C, pH=11.5 After aging at reflux for 50h, filter and dry, and roast at 520°C for 1h. Dissolve a certain amount of RuCl 3 ·xH 2 O in distilled water (the weight of the metal accounts for 8% of the mass of the dispersed carrier), and at the same time add Ni(NO 3 ) 2 according to the molar ratio Ru:Ni=1:0.2, and vacuum impregnate with equal volume Afterwards, it was dried in flowing air at 85°C for 24h, and then reduced at 250°C for 3h in a hydrogen flow of 5ml/min. Catalyst D is obtained.
实施例5 Example 5
ZrOCl2·8H2O与NH3·H2O按照1:3制成沉淀，制成凝胶后，按Zr(OH)4与双氧水比例为1:0.2加入，后在96℃、pH=11.5下老化回流50h后，过滤干燥，并在520℃下焙烧1h得到。将一定量的(NH4)6H2W12O40.xH2O 溶于蒸馏水（与Ru摩尔比为1:10），等体积真空浸渍后，85℃干燥后，并在650℃下焙烧2h。再将一定量的RuCl3·xH2O溶于蒸馏水（以金属质量占分散载体质量的8%），等体积真空浸渍后，置于85℃流动空气中干燥24h，并于20ml/min氢气流中在250℃还原3h。得到催化剂E。 ZrOCl 2 · 8H 2 O and NH 3 · H 2 O were precipitated at a ratio of 1:3. After making a gel, the ratio of Zr(OH) 4 and hydrogen peroxide was added at a ratio of 1:0.2, and then at 96°C, pH=11.5 After aging at reflux for 50h, filter and dry, and roast at 520°C for 1h. A certain amount of (NH 4 ) 6 H 2 W 12 O 40 .xH 2 O was dissolved in distilled water (the molar ratio to Ru was 1:10), vacuum impregnated in equal volume, dried at 85°C, and calcined at 650°C 2h. Dissolve a certain amount of RuCl 3 ·xH 2 O in distilled water (8% of the mass of the dispersed carrier based on the mass of the metal), impregnate in vacuum with equal volume, dry in flowing air at 85°C for 24 hours, and dry at 20ml/min hydrogen flow Reduction at 250°C for 3h. Catalyst E is obtained.
活性选择性测定： Activity selectivity assay:
选取以上实施实例的催化剂进行活性选择性测定，测定在小型高压反应釜中进行，聚四氟内衬。加入100ml水，50ml苯，0.4g催化剂，4.0gZnSO4·7H2O。用氢气置换釜内空气，搅拌速率600rpm。升温速率80℃/h。调节氢压至4.2Mpa，搅拌转速1000rpm，并开始计时。用气相色谱分析油相中苯、环己烯和环己烷的相对百分含量。活性选择性计算方法： The catalysts of the above implementation examples were selected for activity selectivity measurement, and the measurement was carried out in a small high-pressure reactor with a polytetrafluoroethylene lining. Add 100ml of water, 50ml of benzene, 0.4g of catalyst, 4.0g of ZnSO 4 ·7H 2 O. The air in the kettle was replaced with hydrogen, and the stirring rate was 600 rpm. The heating rate is 80°C/h. Regulate the hydrogen pressure to 4.2Mpa, the stirring speed is 1000rpm, and start timing. The relative percentages of benzene, cyclohexene and cyclohexane in the oil phase were analyzed by gas chromatography. Activity selectivity calculation method:
活性：苯转化率（CBZ）=产物中苯的相对浓度*100% Activity: benzene conversion rate (C BZ ) = relative concentration of benzene in the product * 100%
环己烯收率（YHE）=产物中环己烯相对浓度*100% Cyclohexene yield (Y HE ) = relative concentration of cyclohexene in the product * 100%
选择性：环己烯选择性（SHE）=环己烯收率/苯转化率*100%=YHE/CBZ*100% Selectivity: cyclohexene selectivity (S HE ) = cyclohexene yield / benzene conversion * 100% = Y HE /C BZ * 100%
表1给出了反应10、20、30min后，不同的催化剂的活性选择性： Table 1 shows the activity selectivity of different catalysts after reacting for 10, 20, and 30 minutes:
表1 反应10、20、30min时，不同催化剂的活性选择性 Table 1 The activity selectivity of different catalysts when reacting for 10, 20, and 30 minutes
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