CN105498759A - 一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 - Google Patents
一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 Download PDFInfo
- Publication number
- CN105498759A CN105498759A CN201510860897.XA CN201510860897A CN105498759A CN 105498759 A CN105498759 A CN 105498759A CN 201510860897 A CN201510860897 A CN 201510860897A CN 105498759 A CN105498759 A CN 105498759A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetylene
- sba
- palladium
- mcm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 33
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006006 cyclotrimerization reaction Methods 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000010948 rhodium Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 16
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000002808 molecular sieve Substances 0.000 claims abstract description 6
- 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 6
- 239000013335 mesoporous material Substances 0.000 claims abstract description 5
- 238000005899 aromatization reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000005829 trimerization reaction Methods 0.000 claims description 10
- 238000006424 Flood reaction Methods 0.000 claims description 8
- 101150003085 Pdcl gene Proteins 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003283 rhodium Chemical class 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- -1 rhodium transition-metal Chemical class 0.000 abstract description 2
- 238000010792 warming Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 150000001345 alkine derivatives Chemical class 0.000 description 6
- KHKWHTCWOCAWME-UHFFFAOYSA-N acetylene benzene Chemical compound C#C.C1=CC=CC=C1.C#C KHKWHTCWOCAWME-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
-
- 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0354—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
- C07C2/48—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion of only hydrocarbons containing a carbon-to-carbon triple bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
- C07C2529/035—Crystalline silica polymorphs, e.g. silicalites
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
本发明公开了一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用。该催化剂为采用有序介孔材料MCM-41或/和SBA-15为载体制备的负载型高分散钯、钌、铑复合过渡金属催化剂，通过选取结构高度有序的MCM-41及SBA-15介孔分子筛作为载体，采用分步等体积浸渍法制备负载型复合钯、钌、铑过渡金属催化剂。本发明的催化剂利用大比表面有序介孔材料对过渡金属形成较好的分散，有效提高了乙炔环三聚制备苯反应性能。
Description
技术领域
本发明属于化学化工领域，涉及到一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用。
背景技术
苯、甲苯和二甲苯等轻质芳烃(三者统称BTX)作为最基本的有机化工原料，广泛应用于制取橡胶、纤维、塑料、染料等化工产品。目前，芳烃主要来源于石油化工中的催化重整和烃类裂解(约90％)，仅有约10％来源于煤炭化工。近年来，一方面石油资源逐渐减少，另一方面合成材料和其它精细化学品需求的日益增长对芳烃生产形成更高需求，因此开发芳烃生产的新技术势在必行。如果能够利用无环的简单分子，如甲烷、甲醇、乙炔等，使其发生芳构化反应直接转变为高附加值的轻质芳烃，将具有重要的战略意义。
乙炔具有极高的反应活性，其环三聚反应在热力学上是强放热的。但是，该反应在无催化剂参与时需要在400℃的高温下才能发生，且反应仅产生极少量的苯，同时生成大量的副产物。Reppe等人于1948年首次报导(Ann.Chem.1948,560,104)了一种NiBr2催化剂，利用均相催化的手段可以实现炔烃的环三聚反应来合成各种取代苯衍生物。此后，炔烃的芳构化反应引起了国内外研究者们的广泛关注，很多过渡金属及其络合物被发现可以催化乙炔的芳构化反应。
Elsternwick等人(U.S.P.4424401)公开了在沸石催化剂ZSM-5表面，并在惰性气体、水、氢气和醇存在的条件下乙炔芳构化反应性能。在260-550℃的较宽温度范围内，ZSM-5分子筛均可以较好的催化该反应，但极易失活。此后，Timmons等人(U.S.P.5118893)公开了在Ni、Co改性的ZSM-5催化剂表面，并在H2O、H2存在的条件下乙炔发生芳构化反应的情况。结果发现，反应稳定性有一定程度提高，但芳烃选择性降低。A·马马多夫等人(CN101155766A)公开了乙炔在甲烷、二氧化碳和氢气存在条件下，于600-1000℃的范围内不需引入催化剂即可以同时制备苯和乙烯的方法，该方法完全利用热反应，因此反应温度相对较高。
Tysoe等人(J.Chem.Soc.,Chem.Commun.1983,623)和Sesselmann等人(Surf.Sci.1983,135,128)分别报导了过渡金属Pd在低温下具有优异的乙炔环三聚反应性能，发现乙炔在小于210K温度下吸附在Pd(111)单晶催化剂表面后，程序升温过程中约30％的吸附态乙炔发生环三聚反应转化为苯。
综上所述，目前公开报道的乙炔芳构化反应乙炔转化率和苯选择性均较低。虽然研究表明Pd(111)单晶表面具有较好的低温环三聚反应性能，但该过程需要在超高真空条件下进行，难以工业应用。
发明内容
针对上述问题，本发明的目的是提供了一种高性能乙炔环三聚反应制备苯催化剂及其应用，尤其是可以获得100％乙炔转化率和较高的苯选择性。
一种乙炔环三聚制备苯高性能催化剂，该催化剂为采用有序介孔材料MCM-41或/和SBA-15为载体制备的负载型高分散钯/钌/铑复合过渡金属催化剂；负载型高分散过渡金属复合催化剂钯负载量以钯质量记为载体的0.1-2％，钌负载量以钌质量记为载体的0.1-2％，铑负载量以铑质量记为载体的0.1-2％。
一种乙炔环三聚制备苯高性能催化剂的制备方法，按照以下步骤进行：
(1)将MCM-41或/和SBA-15介孔分子筛在空气气氛中500-600℃焙烧4-6h，降至100℃以下放入干燥器备用；
(2)将焙烧预处理过的MCM-41或/和SBA-15介孔分子筛常温等体积加入到钯盐水溶液中浸渍3-12h，然后在空气气氛中110-150℃干燥3-12h，500-600℃焙烧2-6h即得到MCM-41或/和SBA-15负载的钯催化剂；
(3)将MCM-41或/和SBA-15负载的钯催化剂常温等体积加入到钌和铑盐的混合水溶液中浸渍3-12h，然后在空气气氛中110-150℃干燥3-12h，500-600℃焙烧2-6h即得到MCM-41或/和SBA-15负载的钯/钌/铑复合过渡金属催化剂。
所述步骤(2)中钯盐为PdCl2，负载量以Pd质量记为载体的0.1-2％；
所述步骤(3)中钌盐为RuCl3，负载量以Ru质量记为载体的0.1-2％，
所述步骤(3)中铑盐为RhCl3，负载量以Rh质量记为载体的0.1-2％。
一种乙炔环三聚制备苯高性能催化剂的应用，所述催化剂用于乙炔芳构化反应，具体的应用步骤如下：
首先将制备的催化剂装入固定床反应器中，反应前将催化剂在反应装置上氢气气氛中500-600℃原位活化预处理1-3h，使活性组分还原为金属态；。
然后，将包含10-50％体积乙炔和50-90％体积氮气的物料组分通入反应器与预还原后的催化剂接触，并在300-600℃的温度范围及乙炔体积空速300-3000h-1条件下进行芳构化反应。
本发明的效果和益处是：通过选取比表面较大且结构有序的介孔材料MCM-41和SBA-15为载体制备复合负载型钯/钌/铑过渡金属催化剂。一方面，大比表面载体对活性组分形成较好的分散；另一方面，其高度有序的结构特点有利于产物分子扩散，从而有效降低多取代苯等重芳烃的生成。该催化剂在仅有乙炔和氮气参与的条件下使其发生芳构化反应，乙炔转化率达到100％，苯选择性大于80％。本发明操作简单，反应条件较为温和，具有巨大的应用前景。
具体实施方式
下面通过实施例详述本发明，但本发明并不局限于这些实施例。
实施例1
Pd/Ru/Rh/SiO2催化剂的制备
将大孔硅胶在空气气氛中500℃焙烧6h后降至室温，称量50g焙烧过的大孔硅胶载体，等体积加入到PdCl2水溶液中，PdCl2负载量以Pd质量记为大孔硅胶的0.5％，室温下浸渍6h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至500℃焙烧3h即得大孔硅胶负载的Pd/SiO2催化剂，记为Pd(0.5)/SiO2。
然后，将该催化剂等体积加入到RuCl3和RhCl3混合水溶液中，RuCl3和RhCl3负载量以Ru和Rh质量记为大孔硅胶的0.2％和1.3％，室温下浸渍10h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至550℃焙烧5h即得大孔硅胶负载的复合Pd/Ru/Rh/SiO2催化剂，记为Pd(0.5)Ru(0.2)Rh(1.3)/SiO2。经压片、破碎并筛分为20-40目后备用。
实施例2
Pd/Ru/Rh/MCM-41催化剂的制备
将MCM-41在空气气氛中500℃焙烧6h后降至室温，称量50g焙烧过的MCM-41载体，等体积浸渍加入PdCl2水溶液，PdCl2负载量以Pd质量记为MCM-41的0.5％，配置成水溶液后室温下浸渍6h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至550℃焙烧3h即得MCM-41负载的Pd/MCM-41催化剂，记为Pd(0.5)/MCM-41。
将该样品等体积浸渍加入RuCl3和RhCl3的混合水溶液中，RuCl3和RhCl3负载量以Ru和Rh质量均记为MCM-41的0.2％和1.3％，配置成水溶液后室温下浸渍10h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至550℃焙烧5h即得MCM-41负载的复合Pd/Ru/Rh/MCM-41催化剂，记为Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41。经压片、破碎并筛分为20-40目后备用。
实施例3
Pd/Ru/Rh/SBA-15催化剂的制备
将SBA-15在空气气氛中500℃焙烧6h后降至室温，称量50g焙烧过的SBA-15载体，等体积浸渍加入PdCl2水溶液，PdCl2负载量以Pd质量记为SBA-15的0.5％，配置成水溶液后室温下浸渍12h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至550℃焙烧3h即得SBA-15负载的Pd/SBA-15催化剂，记为Pd(0.5)/SBA-15。
将该样品等体积浸渍加入RuCl3和RhCl3的混合水溶液中，RuCl3和RhCl3负载量以Ru和Rh质量均记为SBA-15的0.5％和1％，配置成水溶液后室温下浸渍6h。所得的混合物在110℃温度下烘干后，在空气气氛中10℃/min升温至550℃焙烧5h即得SBA-15负载的复合Pd/Ru/Rh/SBA-15催化剂，记为Pd(0.5)Ru(0.5)Rh(1)/SBA-15。经压片、破碎并筛分为20-40目后备用。
实施例4
反应评价
乙炔芳构化反应在固定床反应装置上进行，使用内径10mm不锈钢反应器，反应压力常压。分别将2g实施例1-3制备的Pd(0.5)Ru(0.2)Rh(1.3)/SiO2、Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41及Pd(0.5)Ru(0.5)Rh(1)/SBA-15装入反应器中，在氢气气氛中10℃/min升温至500℃并保持2h。还原之后切换为N2气氛吹扫1h，然后通入10％C2H2+90％N2(体积组成)的反应气，反应气体空速为600h-1。实验中气体的流量均由质量流量计控制，反应产物利用配备双FID检测器的气相色谱仪对其在线分析，反应结果列于表1-3中。
结果表明，有序介孔材料负载的复合Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41和Pd(0.5)Ru(0.5)Rh(1)/SBA-15催化剂较大孔硅胶负载的Pd(0.5)Ru(0.2)Rh(1.3)/SiO2催化剂具有更高的乙炔转化率和苯选择性。
实施例5
反应评价
乙炔芳构化反应在固定床反应装置上进行，使用内径10mm不锈钢反应器，反应压力常压。将2g实施例2制备的Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41装入反应器中，在氢气气氛中10℃/min升温至500℃并保持2h。还原之后切换为N2气氛吹扫1h，再降温至450℃后通入30％C2H2+70％N2(体积组成)的反应气，反应气体空速为1800h-1。实验中气体的流量均由质量流量计控制，反应产物利用配备双FID检测器的气相色谱仪对其在线分析，反应结果列于表4中。
实施例6
反应评价
乙炔芳构化反应在固定床反应装置上进行，使用内径10mm不锈钢反应器，反应压力常压。将2g实施例3制备的Pd(0.5)Ru(0.5)Rh(1)/SBA-15装入反应器中，在氢气气氛中10℃/min升温至500℃并保持2h。还原之后切换为N2气氛吹扫1h，再升温至550℃后通入50％C2H2+50％N2(体积组成)的反应气，反应气体空速为3000h-1。实验中气体的流量均由质量流量计控制，反应产物利用配备双FID检测器的气相色谱仪对其在线分析，反应结果列于表5中。
表1Pd(0.5)Ru(0.2)Rh(1.3)/SiO2催化剂乙炔制苯反应结果
表2Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41催化剂乙炔制苯反应结果
表3Pd(0.5)Ru(0.5)Rh(1)/SBA-15催化剂乙炔制苯反应结果
表4Pd(0.5)Ru(0.2)Rh(1.3)/MCM-41催化剂乙炔制苯反应结果
表5Pd(0.5)Ru(0.5)Rh(1)/SBA-15催化剂乙炔制苯反应结果
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据发明技术实质所作的改变和修改均仍属于保护范围内。
Claims (4)
1.一种乙炔环三聚制备苯高性能催化剂，其特征在于，该催化剂为采用有序介孔材料MCM-41或/和SBA-15为载体制备的负载型高分散钯/钌/铑复合过渡金属催化剂；负载型高分散过渡金属复合催化剂钯负载量以钯质量记为载体的0.1-2％，钌负载量以钌质量记为载体的0.1-2％，铑负载量以铑质量记为载体的0.1-2％。
2.根据权利要求1所述的一种乙炔环三聚制备苯高性能催化剂的制备方法，其特征在于按照以下步骤进行：
(1)将MCM-41或/和SBA-15介孔分子筛在空气气氛中500-600℃焙烧4-6h，降温至100℃以下放入干燥器中备用；
(2)将焙烧预处理过的MCM-41或/和SBA-15介孔分子筛常温等体积加入到钯盐水溶液中浸渍3-12h，然后在空气气氛中110-150℃干燥3-12h，500-600℃焙烧2-6h即得到MCM-41或/和SBA-15负载的钯催化剂；
(3)将MCM-41或/和SBA-15负载的钯催化剂常温等体积加入到钌和铑盐的混合水溶液中浸渍3-12h，然后在空气气氛中110-150℃干燥3-12h，500-600℃焙烧2-6h即得到MCM-41或/和SBA-15负载的钯/钌/铑复合过渡金属催化剂。
3.根据权利要求2所述的一种乙炔环三聚制备苯高性能催化剂的制备方法，其特征在于：
所述步骤(2)中钯盐为PdCl2，负载量以Pd质量记为载体的0.1-2％；
所述步骤(3)中钌盐为RuCl3，负载量以Ru质量记为载体的0.1-2％，
所述步骤(3)中铑盐为RhCl3，负载量以Rh质量记为载体的0.1-2％。
4.根据权利要求1所述的一种乙炔环三聚制备苯高性能催化剂的应用，其特征在于所述催化剂用于乙炔芳构化反应，具体的应用步骤如下：
首先将制备的催化剂装入固定床反应器中，反应前将催化剂在反应装置上氢气气氛中500-600℃原位活化预处理1-3h，使活性组分还原为金属态；
然后，将包含10-50％体积乙炔和50-90％体积氮气的物料组分通入反应器与预还原后的催化剂接触，并在300-600℃的温度范围及乙炔体积空速300-3000h-1条件下进行芳构化反应。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510860897.XA CN105498759B (zh) | 2015-12-01 | 2015-12-01 | 一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510860897.XA CN105498759B (zh) | 2015-12-01 | 2015-12-01 | 一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105498759A true CN105498759A (zh) | 2016-04-20 |
| CN105498759B CN105498759B (zh) | 2018-03-16 |
Family
ID=55707293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510860897.XA Expired - Fee Related CN105498759B (zh) | 2015-12-01 | 2015-12-01 | 一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105498759B (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107042120A (zh) * | 2017-05-26 | 2017-08-15 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其制备方法和应用 |
| CN107051588A (zh) * | 2017-05-26 | 2017-08-18 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其使用方法 |
| CN107570204A (zh) * | 2017-09-18 | 2018-01-12 | 北京华福工程有限公司 | 乙炔环三聚制苯用催化剂及其制备方法和应用 |
| CN107603668A (zh) * | 2017-09-01 | 2018-01-19 | 北京华福工程有限公司 | 乙炔三聚生产轻质芳烃的方法 |
| CN115055201A (zh) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | 一种乙炔芳构化反应制备苯的催化剂及其制备和应用 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199478A (en) * | 1977-02-01 | 1980-04-22 | Snamprogetti S.P.A. | Method for preparing metal-carbonyl clusters immobilized in zeolite, as heterogeneous catalysts |
| US20040081611A1 (en) * | 2002-10-25 | 2004-04-29 | Basf Akiengesellschaft | Process for preparing hydrogen peroxide from the elements |
| WO2004045767A2 (en) * | 2002-11-20 | 2004-06-03 | Exxonmobil Research And Engineering Company | Methods for preparing catalysts |
| CN101006162A (zh) * | 2004-07-08 | 2007-07-25 | Abb路慕斯全球股份有限公司 | 使用中孔催化剂氢化芳烃和烯烃 |
| CN101795999A (zh) * | 2007-07-24 | 2010-08-04 | 埃克森美孚化学专利公司 | 由脂族化合物制备芳族化合物 |
| CN102240570A (zh) * | 2010-05-11 | 2011-11-16 | 北京化工大学 | 一种具有介孔特征催化剂及其应用 |
| CN104588006A (zh) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | 一种用于炔烃选择加氢的含钯的合金单原子催化剂 |
-
2015
- 2015-12-01 CN CN201510860897.XA patent/CN105498759B/zh not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199478A (en) * | 1977-02-01 | 1980-04-22 | Snamprogetti S.P.A. | Method for preparing metal-carbonyl clusters immobilized in zeolite, as heterogeneous catalysts |
| US20040081611A1 (en) * | 2002-10-25 | 2004-04-29 | Basf Akiengesellschaft | Process for preparing hydrogen peroxide from the elements |
| WO2004045767A2 (en) * | 2002-11-20 | 2004-06-03 | Exxonmobil Research And Engineering Company | Methods for preparing catalysts |
| CN101006162A (zh) * | 2004-07-08 | 2007-07-25 | Abb路慕斯全球股份有限公司 | 使用中孔催化剂氢化芳烃和烯烃 |
| CN101795999A (zh) * | 2007-07-24 | 2010-08-04 | 埃克森美孚化学专利公司 | 由脂族化合物制备芳族化合物 |
| CN102240570A (zh) * | 2010-05-11 | 2011-11-16 | 北京化工大学 | 一种具有介孔特征催化剂及其应用 |
| CN104588006A (zh) * | 2013-10-31 | 2015-05-06 | 中国科学院大连化学物理研究所 | 一种用于炔烃选择加氢的含钯的合金单原子催化剂 |
Non-Patent Citations (2)
| Title |
|---|
| 程金生等: ""过渡金属催化的炔烃芳构化反应"", 《有机化学》 * |
| 程金生等: ""钯催化的炔烃芳构化反应研究"", 《广州化学》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107042120A (zh) * | 2017-05-26 | 2017-08-15 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其制备方法和应用 |
| CN107051588A (zh) * | 2017-05-26 | 2017-08-18 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其使用方法 |
| CN107042120B (zh) * | 2017-05-26 | 2019-10-29 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其制备方法和应用 |
| CN107051588B (zh) * | 2017-05-26 | 2019-10-29 | 北京华福工程有限公司 | 一种乙炔三聚制苯催化剂及其使用方法 |
| CN107603668A (zh) * | 2017-09-01 | 2018-01-19 | 北京华福工程有限公司 | 乙炔三聚生产轻质芳烃的方法 |
| CN107603668B (zh) * | 2017-09-01 | 2020-07-03 | 北京华福工程有限公司 | 乙炔三聚生产轻质芳烃的方法 |
| CN107570204A (zh) * | 2017-09-18 | 2018-01-12 | 北京华福工程有限公司 | 乙炔环三聚制苯用催化剂及其制备方法和应用 |
| CN115055201A (zh) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | 一种乙炔芳构化反应制备苯的催化剂及其制备和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105498759B (zh) | 2018-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qiu et al. | A simple method to prepare highly active and dispersed Ni/MCM-41 catalysts by co-impregnation | |
| CN101890351B (zh) | 蛋壳型镍基催化剂 | |
| Huang et al. | Selective hydrogenation of acetylene in the presence of ethylene on zeolite-supported bimetallic catalysts | |
| CN107088436B (zh) | 乙炔选择性加氢制备乙烯的催化剂及制备方法和应用 | |
| CN105498759A (zh) | 一种乙炔环三聚制备苯高性能催化剂及其制备方法和应用 | |
| Chakrabarti et al. | Conversion of CO2 over a co-based Fischer–Tropsch catalyst | |
| CN105498757B (zh) | 一种乙炔环三聚制备苯的催化剂及制备苯的方法 | |
| CN105728020B (zh) | 一种核壳型碳化铁催化剂制备方法 | |
| CN111514927B (zh) | 金属碳化物纳米材料催化剂及其制备方法 | |
| CN105712817B (zh) | 一种对甲基环己烯甲醛选择制备对二甲苯和甲苯的方法 | |
| Jan et al. | Liquid hydrocarbon production via ethylene oligomerization over Ni-Hβ | |
| CN109569704A (zh) | 一种用于合成气直接制备烯烃和芳烃的催化剂及其应用 | |
| CN106975486A (zh) | 一种co加氢制低碳混合醇的催化剂及其制备方法 | |
| Wang et al. | Tuning electronic structure of palladium from wheat flour-derived N-doped mesoporous carbon for efficient selective hydrogenation of acetylene | |
| Jin et al. | Effect of CO2 on the catalytic performance of Zn/ZSM-5 towards the conversion of methanol to aromatics | |
| Zhang et al. | Tuning the mesopore-acid-metal balance in Pd/HY for efficient deep hydrogenation saturation of naphthalene | |
| Yan et al. | Visualizing the birth and monitoring the life of a bimetallic methanation catalyst | |
| Cao et al. | Size effect in propane dehydrogenation on PtIn/Sn-SBA-15 | |
| Zhou et al. | Unraveling Active Ni Sites over Dealuminated β Zeolite for Propane Dehydrogenation | |
| CN109433252B (zh) | 一种co2氧化c2h6脱氢制c2h4的催化剂及其制备方法 | |
| CN109433257B (zh) | 一种二氧化碳氧化乙烷脱氢制乙烯的催化剂及其制备方法 | |
| CN107042120B (zh) | 一种乙炔三聚制苯催化剂及其制备方法和应用 | |
| CN104178204B (zh) | 一种富含异构烷烃汽油的制备方法 | |
| Liu et al. | Catalytic performance of coal tar by step conversion of single-component, multi-components, distillate and all-distillates over bifunctional HZSM-5: Model optimization and experiment verification | |
| CN115055201B (zh) | 一种乙炔芳构化反应制备苯的催化剂及其制备和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180316 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |