CN117816231A - Catalyst for isomerisation of dichlorotoluene - Google Patents
Catalyst for isomerisation of dichlorotoluene Download PDFInfo
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- CN117816231A CN117816231A CN202311526137.6A CN202311526137A CN117816231A CN 117816231 A CN117816231 A CN 117816231A CN 202311526137 A CN202311526137 A CN 202311526137A CN 117816231 A CN117816231 A CN 117816231A
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- dichlorotoluene
- molecular sieve
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- earth metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 47
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 title abstract description 13
- KFAKZJUYBOYVKA-UHFFFAOYSA-N 1,4-dichloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Cl KFAKZJUYBOYVKA-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- 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 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 150000007524 organic acids Chemical class 0.000 claims abstract description 20
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 19
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims description 29
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000012159 carrier gas Substances 0.000 claims description 20
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 3
- 239000011575 calcium Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000012847 fine chemical Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYUIWKFIFOJVKW-UHFFFAOYSA-N 1,2-dichloro-4-methylbenzene Chemical group CC1=CC=C(Cl)C(Cl)=C1 WYUIWKFIFOJVKW-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- UZPZYFDULMKDMB-UHFFFAOYSA-N 1,2-dichloro-3,4-dimethylbenzene Chemical group CC1=CC=C(Cl)C(Cl)=C1C UZPZYFDULMKDMB-UHFFFAOYSA-N 0.000 description 1
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical group CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- JHSPCUHPSIUQRB-UHFFFAOYSA-N 2,6-dichlorobenzamide Chemical compound NC(=O)C1=C(Cl)C=CC=C1Cl JHSPCUHPSIUQRB-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 239000003430 antimalarial agent Substances 0.000 description 1
- -1 aromatic chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical class ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- FBOUIAKEJMZPQG-BLXFFLACSA-N diniconazole-M Chemical compound C1=NC=NN1/C([C@H](O)C(C)(C)C)=C/C1=CC=C(Cl)C=C1Cl FBOUIAKEJMZPQG-BLXFFLACSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
The invention discloses a 2, 5-dichlorotoluene isomerization catalyst, wherein the carrier of the catalyst is a hierarchical pore hydrogen molecular sieve, the active component is zirconia, the cocatalyst is alkaline earth metal oxide, the total loading amount of the zirconia and the alkaline earth metal oxide is 1-5wt%, and the molar ratio of the zirconia to the alkaline earth metal is 10:0-0:10; the hierarchical porous hydrogen molecular sieve is obtained by modifying hydrogen molecular sieve with organic acid. The mesoporous pore canal can be effectively constructed in the molecular sieve crystal through dealumination modification of the organic acid, the specific surface area, the mesoporous pore diameter, the pore volume and the like of the molecular sieve are increased, the diffusion of macromolecules in the pore canal is greatly enhanced, and the carbon deposition deactivation of the catalyst is inhibited; the active component can provide more catalytic active sites, so that the catalytic activity of the catalyst is improved, and the promoter has positive influence on the acid property, carbon deposition and the like of the catalyst; the highest conversion rate of the 2, 5-dichlorotoluene reaches 59.14 percent, and the total selectivity of the dichlorotoluene reaches 37.77 percent.
Description
Technical Field
The invention belongs to the field of the isomerization of chlorotoluene derivatives and the application field of metal-molecular sieve dual-function catalysts, relates to a dichlorotoluene isomerization catalyst, and in particular relates to a catalyst for the isomerization reaction of 2, 5-dichlorotoluene.
Background
Among the dichlorotoluene isomers, 2, 5-dichlorotoluene has a narrow application range and low price, while 2, 4-dichlorotoluene is an important fine chemical intermediate, is widely applied to industries such as pesticides, medicines and dyes, and can be used for synthesizing herbicides such as pyrazolidine, bactericides such as diniconazole, ciprofloxacin and antimalarial drug such as amipine. The usual preparation methods of 2, 4-dichlorotoluene are: the direct chlorination method of p-chlorotoluene, the diazotization method of 3-chloro-p-toluidine and the like, but the methods have the defects of more byproducts, complex process, larger pollution and the like.
2, 6-dichlorotoluene is widely used as an important fine chemical raw material in the fields of pesticides, medicines, dyes and the like to prepare pesticides, bactericides, dyes, medicines and other chemical products. For example, 2, 6-dichlorobenzonitrile, 2, 6-dichlorobenzamide, 2, 6-dichlorophenol, some asymmetric biphenyl derivatives and other fine chemical products can be synthesized by taking 2, 6-dichlorobenzene as a reaction intermediate.
At present, a plurality of methods for synthesizing 2, 6-dichlorotoluene exist at home and abroad, wherein the main synthesis methods include an ortho-or para-nitrotoluene method, an ortho-or para-methylsulfonyl chloride method, a toluene direct chlorination method, an ortho-chlorotoluene method, a dichlorotoluene isomerization method and the like. The method has simple reaction steps, is favorable for industrialization, but can be used as a byproduct of 2, 5-dichlorotoluene and 2, 4-dichlorotoluene simultaneously, and the byproduct containing the 2, 5-dichlorotoluene can not be separated because the boiling points of the 2, 5-dichlorotoluene and the 2, 4-dichlorotoluene are extremely close, so that the byproduct containing the 2, 5-dichlorotoluene can only be used as a solvent, and the added value of the byproduct is greatly reduced. And isomerization of 2, 5-dichlorotoluene to other structures of dichlorotoluene is a viable route to increase the added value of 2, 5-dichlorotoluene.
The isomerization method takes 2, 5-dichlorotoluene isomer as raw material, and adopts proper catalyst and excellent reaction process to make isomerization reaction to prepare other isomers of 2, 6-dichlorotoluene, etc. Therefore, in order to maintain the healthy and sustainable development of the fine chemistry industry in China, proper catalysts and process parameters are screened, and the research and development of synthetic routes and production processes of isomers such as 2, 6-dichlorotoluene and the like are enhanced, so that the method has important research significance and wide application prospect.
The JPS6393739a patent provides a method for isomerising aromatic chlorides using the acid form of the omega zeolite as a catalyst, which is found to have a more excellent catalytic activity and reaction selectivity, which can increase the concentration of certain isomers in the dichlorotoluene mixture. When omega zeolite in acid form is used as catalyst, the reaction temperature is 300 ℃ and the mass space velocity is 0.6hr -1 Under the optimal conditions, the content of 2, 5-dichlorotoluene in the component is reduced from 60.3% to 54.4%, and the content of 2, 6-dichlorotoluene is increased from 0.92% to 5.99%.
Chinese patent application CN 105198696A discloses a method for preparing 2, 6-dichlorotoluene by catalyzing 2, 5-dichlorotoluene with H-type molecular sieve, under normal pressure, when H beta molecular sieve is used, the volume space velocity of 2, 5-dichlorotoluene is 0.6hr at the reaction temperature of 350 DEG C -1 When the flow rate of the nitrogen carrier gas was 10mL/min, the conversion of 2, 5-dichlorotoluene was 30.9%, and the selectivity of 2, 6-dichlorotoluene was 45.7%.
Chinese patent CN 112705186 A adopts heteroatom doped modified carbon source as 2, 5-dichlorotoluene isomerization catalyst, when the reaction temperature is 360 ℃, the volume space velocity of 2, 5-dichlorotoluene is 0.44hr -1 At a nitrogen carrier gas flow rate of 20mL/min, the 2, 5-dichlorotoluene conversion was 44.6% and the 2, 6-dichlorotoluene selectivity was 32.2%.
The method mostly adopts a hydrogen type molecular sieve as a catalyst to convert the 2, 5-dichlorotoluene with low added value into the 2, 4-dichlorotoluene or the 2, 6-dichlorotoluene with high added value, but the conversion rate is generally lower.
Supported catalysts are generally composed of a molecular sieve support and an active component, wherein the usual active component is a metal species. The supported metal catalyst has high catalytic activity, selectivity and stability, small corrosiveness, can be continuously recovered and reused, is widely applied to petroleum refining and petrochemical processes, and is an important catalytic material in catalytic reactions such as hydrogenation, dehydrogenation and isomerization. However, the relatively small pore diameter of the microporous molecular sieve is unfavorable for the diffusion of macromolecular reactants and products in pore channels, and carbon deposition deactivation of the molecular sieve is easy to cause, so that the catalytic activity, the service life and the like of the catalyst are reduced.
Disclosure of Invention
The invention aims to develop a 2, 5-dichlorotoluene isomerization catalyst which has low production cost and is easy for industrial production.
The invention aims at realizing the following technical scheme:
the catalyst has carrier of hierarchical porous hydrogen molecular sieve, active component of zirconia, promoter of alkaline earth metal oxide, total load of zirconia and alkaline earth metal oxide (the mass of the metal oxide accounts for the total mass of the molecular sieve) of 1-5 wt% and molar ratio of zirconium to alkaline earth metal of 10:0-0:10.
The hierarchical pore hydrogen type molecular sieve is obtained by modifying a hydrogen type molecular sieve with an organic acid source.
The hierarchical pore hydrogen type molecular sieve is prepared by the following method: immersing hydrogen molecular sieve in organic acid aqueous solution, reacting for 1-3 h at 70-90 ℃, filtering, washing the obtained solid with deionized water to neutrality, drying at 100-120 ℃, and roasting at 550 ℃ for 2-4 h to obtain the hierarchical pore hydrogen molecular sieve.
The hydrogen type molecular sieve is H beta molecular sieve, preferably SiO 2 /Al 2 O 3 Hβ molecular sieves=30. The particle size of the hydrogen type molecular sieve is 30-60 meshes.
The concentration of the aqueous organic acid solution is 5 to 40wt%, preferably 15wt%.
The organic acid is any one of acetic acid, citric acid and oxalic acid, preferably oxalic acid.
The feed liquid ratio of the hydrogen type molecular sieve leaching to the organic acid aqueous solution is 1:10g/mL.
The alkaline earth metal is Ca; the alkaline earth metal oxide is CaO.
Preferably, the total loading of zirconia and alkaline earth metal oxide is 3wt%.
Preferably, the molar ratio of the zirconium to the alkaline earth metal is 7:3-3:7.
More preferably, the molar ratio of zirconium to alkaline earth metal is 7:3 to 5:5.
Most preferably, the molar ratio of zirconium to alkaline earth metal is 7:3.
Specifically, the molar ratio of zirconium to alkaline earth metal is 10:0, 7:3, 5:5, 3:7, 0:10.
Another object of the present invention is to provide a method for preparing the 2, 5-dichlorotoluene isomerization catalyst, comprising the steps of:
immersing a hydrogen type molecular sieve in an organic acid aqueous solution, reacting for 1-3 hours at the temperature of 70-90 ℃, filtering, washing the obtained solid with deionized water to be neutral, drying at the temperature of 100-120 ℃, and roasting at the temperature of 550 ℃ for 2-4 hours to obtain the multi-stage pore hydrogen type molecular sieve;
step (2), zr (NO) 3 ) 4 ·5H 2 O and alkaline earth metal nitrate are dissolved in deionized water to obtain a mixed solution; mixing the mixed solution with a hierarchical pore hydrogen type molecular sieve,soaking for 12-24 h, filtering, drying the solid at 110-120 ℃, and roasting at 450-550 ℃ for 3-5 h to obtain the 2, 5-dichlorotoluene isomerization catalyst.
The alkaline earth metal nitrate is Ca (NO) 3 ) 2 ·4H 2 O。
The temperature of the soaking is normal temperature.
The invention also aims to provide the application of the catalyst for preparing 2, 4-dichlorotoluene and 2, 6-dichlorotoluene by catalyzing 2, 5-dichlorotoluene isomerization.
A process for preparing 2, 4-dichlorotoluene and 2, 6-dichlorotoluene by catalytic isomerization of 2, 5-dichlorotoluene, comprising: takes 2, 5-dichlorotoluene as raw material and N 2 The catalyst is used as carrier gas, the 2, 5-dichlorotoluene isomerization catalyst is used as catalyst, the mass airspeed of the raw material is 0.3-1.0 hr -1 The flow rate of the carrier gas is 6.5-20 mL/min/gcat, and the 2, 5-dichlorotoluene is subjected to isomerization reaction at the reaction temperature of 330-370 ℃ to produce 2, 4-dichlorotoluene and 2, 6-dichlorotoluene.
Preferably, the reaction temperature is 340-360 ℃.
Most preferably, the reaction temperature is 350 ℃.
Preferably, the mass space velocity of the raw materials is 0.4-0.8 hr -1 。
Most preferably, the feedstock has a mass space velocity of 0.4hr -1 。
Preferably, the flow rate of the carrier gas is 6.5-7 mL/min/gcat.
Feed mass space velocity = feed mass flow/catalyst mass.
The invention has the beneficial effects that:
according to the invention, through dealumination modification of the organic acid, mesoporous pore channels can be effectively constructed in the H beta molecular sieve crystal, and the H beta molecular sieve pore channels are enlarged, so that the specific surface area, the mesoporous pore diameter, the pore volume and the like of the molecular sieve are increased, the diffusion of macromolecules in the pore channels is greatly enhanced, and the carbon deposition deactivation of the catalyst is greatly inhibited. The metal active component loaded by the catalyst can provide more catalytic active sites, so that the catalytic activity of the catalyst is improved, and meanwhile, the addition of the promoter alkaline earth metal oxide has positive influence on the acid property, carbon deposit effect and the like of the catalyst, and the catalytic activity of the catalyst is further enhanced.
The catalyst of the invention is used for catalyzing the isomerization reaction of the 2, 5-dichlorotoluene, the highest conversion rate of the 2, 5-dichlorotoluene can reach 59.14 percent, and the total selectivity of the dichlorotoluene can reach 37.77 percent.
Detailed Description
The technical scheme of the present invention will be further described in detail with reference to examples, but the embodiments of the present invention are not limited thereto, and the data shown therein do not represent limitations on the scope of the features of the present invention.
Example 1
The preparation of the hierarchical pore hydrogen type molecular sieve comprises the following steps:
20g of organic acid solid (acetic acid, citric acid or oxalic acid) was added to 80g of deionized water, and the mixture was stirred and mixed well to prepare an aqueous solution of organic acid having a concentration of 20 wt%. 10gH beta molecular sieves (SiO 2 /Al 2 O 3 30, hereinafter abbreviated as hβ30, particle size of 30-60 mesh) is immersed in the above organic acid aqueous solution, stirred and refluxed at 80 ℃ for 2H, filtered, the obtained solid is washed with deionized water until the filtrate is neutral, dried at 110 ℃ for 12H, and finally calcined at 550 ℃ for 3H, thereby obtaining the hierarchical pore hydrogen molecular sieve (respectively denoted as acetic acid modified hβ, citric acid modified hβ, oxalic acid modified hβ).
2, 5-dichlorotoluene (2, 5-DCT) is taken as a raw material to carry out 2, 5-dichlorotoluene gas phase isomerization reaction, the influence of organic acids on catalyzing the 2, 5-dichlorotoluene isomerization reaction by an H beta molecular sieve is examined, and the reaction conditions are as follows: the raw material mass space velocity is 0.8hr -1 Carrier gas N 2 The flow rate was 10.87mL/min/gcat, the reaction temperature was 350℃and the reaction time was 1h.
The reaction results are shown in Table 1, and compared with the H beta molecular sieve, the selectivity of the catalyst modified by using the organic acid as the acid source to the 2, 6-dichlorotoluene and the 2, 4-dichlorotoluene is improved; in particular, when the catalyst modified by using oxalic acid as an acid source was most effective, the conversion of 2, 5-dichlorotoluene was 41.19%, the selectivity of 2, 6-dichlorotoluene was 18.99% and the selectivity of 2, 4-dichlorotoluene was 12.71%.
TABLE 1 influence of organic acid species on raw material conversion and product selectivity
Note that: CB is chlorobenzene, o-CT is o-chlorotoluene, DCB is dichlorobenzene, DCX is dichloroxylene, 2,3-DCT is 2, 3-dichlorotoluene, 2,4-DCT is 2, 4-dichlorotoluene, 2,6-DCT is 2, 6-dichlorotoluene, and 3,4-DCT is 3, 4-dichlorotoluene.
Example 2
The preparation of the hierarchical pore hydrogen type molecular sieve comprises the following steps:
adding oxalic acid solid into deionized water, and uniformly stirring and mixing to obtain oxalic acid aqueous solutions with the concentrations of 5, 10, 15, 20, 25 and 30wt percent respectively; 10g H beta molecular sieves (SiO 2 /Al 2 O 3 =30, particle size 30-60 mesh) was immersed in an aqueous oxalic acid solution (solid-to-liquid ratio 1:10 g/mL), stirred at 80 ℃ for reflux reaction for 2H, filtered, the solids were washed with deionized water until the filtrate was neutral to remove oxalic acid, the resulting solids were dried at 110 ℃ for 12H, and then calcined at 550 ℃ for 3H to give a hierarchical pore hydrogen molecular sieve, designated C-hβ -x (x represents oxalic acid solution concentration).
Taking 2, 5-dichlorotoluene (2, 5-DCT) as a raw material, examining the influence of oxalic acid concentration on H beta molecular sieve catalytic 2, 5-dichlorotoluene isomerization reaction, and the reaction conditions are as follows: the raw material mass space velocity is 0.8hr -1 Carrier gas N 2 The flow rate was 10.87mL/min/gcat, the reaction temperature was 350℃and the reaction time was 1h.
The reaction results are shown in Table 2, and it can be seen that the conversion rate of 2, 5-dichlorotoluene and the selectivity of 2, 6-dichlorotoluene and 2, 4-dichlorotoluene of the catalyst modified by using oxalic acid as an acid source are improved compared with the H beta molecular sieve; with the increase of oxalic acid concentration, the conversion rate of 2, 5-dichlorotoluene is increased and then decreased, and the selectivity of 2, 4-dichlorotoluene and 2, 6-dichlorotoluene is decreased and then increased, which is opposite to the increasing trend of the conversion rate. Wherein, the catalyst has the best catalytic performance when the oxalic acid concentration is 15%, the conversion rate of 2, 5-dichlorotoluene is 43.33%, the selectivity of 2, 6-dichlorotoluene is 19.45%, and the selectivity of 2, 4-dichlorotoluene is 12.72%.
TABLE 2 influence of oxalic acid concentration on raw material conversion and product selectivity
Example 3
The preparation of the bimetal modified hierarchical pore hydrogen type molecular sieve comprises the following steps:
using the hierarchical pore hydrogen molecular sieve C-H beta-15 prepared under the optimal oxalic acid concentration of example 2 as a catalyst carrier, zr (NO) 3 ) 4 ·5H 2 O and calcium nitrate are dissolved in deionized water according to a certain proportion, and mixed solution of zirconium nitrate and calcium nitrate is obtained after complete dissolution; mixing the mixed solution of zirconium nitrate and calcium nitrate with 10g of hierarchical pore hydrogen type molecular sieve, soaking for 24 hours at normal temperature, filtering, drying the obtained solid at the temperature of 110 ℃ for 12 hours, and roasting at the temperature of 550 ℃ for 4 hours to obtain the bimetal modified hierarchical pore molecular sieve, wherein the total loading amount of zirconium oxide and calcium oxide on the catalyst is 3wt%, and the mole ratio of Zr and Ca is shown in table 3.
The conditions of the 2, 5-dichlorotoluene isomerization reaction are the same as those of the example 1, the metal molar ratio in the catalyst is changed, the influence of the metal molar ratio in the catalyst on the isomerization reaction process of the 2, 5-dichlorotoluene catalyzed by the bimetallic modified multi-stage hydrogen molecular sieve is examined, and the reaction results are shown in table 3. It can be seen that the supported bimetallic Zr-Ca can effectively improve the catalytic activity of the catalyst compared with C-H beta-15. With the reduction of the Zr/Ca molar ratio, the conversion rate of the 2, 5-dichlorotoluene is firstly increased and then reduced; wherein, when the mole ratio of Zr to Ca is 7:3, the catalyst has the best catalytic performance, the conversion rate of 2, 5-dichlorotoluene is 49.81 percent, the selectivity of 2, 6-dichlorotoluene is 19.83 percent, and the selectivity of 2, 4-dichlorotoluene is 13.02 percent.
TABLE 3 influence of the molar ratio of metals on the conversion of the starting materials and the selectivity of the products
Note that: zr: the molar ratio of Ca is 10:0 represents a zirconia loading of 3wt%, zr: the molar ratio of Ca is 0:10 represents a calcium oxide loading of 3wt%.
Example 4
The conditions for the isomerization of 2, 5-dichlorotoluene were the same as those of example 1, and a 7Zr:3Ca-Hβ catalyst (bimetallic modified hierarchical pore hydrogen molecular sieve having a molar ratio of Zr to Ca of 7:3 prepared in example 3) was used, and the mass space velocity of 2, 5-dichlorotoluene was 0.8hr -1 Carrier gas N 2 When the flow rate was 10.87mL/min/gcat, the reaction temperature was changed to 330℃at 340℃at 350℃at 360℃at 370℃respectively, and the influence of the reaction temperature on the isomerization reaction process of 2, 5-dichlorotoluene catalyzed by the modified H.beta.molecular sieve was examined, and the reaction results are shown in Table 4.
It was shown that as the reaction temperature was increased, the conversion of 2, 5-dichlorotoluene was increased and then decreased, and the selectivity of 2, 4-dichlorotoluene and 2, 6-dichlorotoluene was gradually decreased. Wherein, when the reaction temperature is 350 ℃, the modified H beta molecular sieve catalyst has the optimal catalytic activity on the 2, 5-dichlorotoluene isomerization reaction, the conversion rate of the 2, 5-dichlorotoluene reaches the highest, the selectivity of the 2, 6-dichlorotoluene is 19.73%, and the selectivity of the 2, 4-dichlorotoluene is 13.06%.
TABLE 4 influence of reaction temperature on the conversion of raw materials and the selectivity of the products
Example 5
Isomerisation reaction of 2, 5-dichlorotolueneThe conditions were the same as in example 1, using a 7Zr:3 Ca-H.beta.catalyst, carrier gas N 2 The flow rate is 10.87mL/min/gcat, the reaction temperature is 350 ℃, and the mass airspeed of the raw material 2, 5-dichlorotoluene is changed to be 0.3hr respectively -1 、0.4hr -1 、0.6hr -1 、0.8hr -1 、1.0hr -1 The influence of the mass space velocity of the raw material on the isomerization reaction process of the 2, 5-dichlorotoluene catalyzed by the modified H beta molecular sieve is examined, and the reaction result is shown in table 5.
Experimental results show that when the raw material mass space velocity is from 0.3hr -1 Increasing to 1.0hr -1 At the time, the conversion rate of the 2, 5-dichlorotoluene is gradually reduced from 60.21 percent to 39.29 percent, and the conversion rate is reduced due to the shortened contact time of the raw materials and the catalyst caused by the increase of the mass airspeed of the raw materials; the selectivity of the 2, 6-dichlorotoluene, the 2, 4-dichlorotoluene and the dichlorotoluene is increased along with the increase of the mass airspeed of the raw materials. Therefore, the method can find that the raw material has higher 2, 5-dichlorotoluene conversion rate when the mass space velocity is lower, but side reaction is also aggravated, so that the isomerization degree of 2, 5-dichlorotoluene is reduced, the number of dichlorotoluene isomers is reduced, and more byproducts such as dichlorobenzene and the like are generated.
When the raw material mass space velocity is 0.4hr -1 When the catalyst is used, the catalyst has good catalytic activity. At this time, the conversion of 2, 5-dichlorotoluene was 57.47%, the selectivity for 2, 6-dichlorotoluene was 18.77%, and the selectivity for 2, 4-dichlorotoluene was 13.31%.
TABLE 5 influence of feedstock mass space velocity on feedstock conversion and product selectivity
Example 6
The conditions for the isomerisation reaction of 2, 5-dichlorotoluene were the same as those of example 1, using a 7Zr:3Ca-H beta catalyst, starting materialThe mass space velocity of 2, 5-dichlorotoluene is 0.4hr -1 The reaction temperature is 350 ℃, and the carrier gas N is changed 2 When the flow rates were 6.52mL/min/gcat, 10.87mL/min/gcat, 15.22mL/min/gcat and 19.57mL/min/gcat, respectively, the influence of the carrier gas flow rate on the isomerization reaction process of the modified H beta molecular sieve catalyzed 2, 5-dichlorotoluene was examined, and the reaction results are shown in Table 6.
Experimental results show that when carrier gas N 2 When the flow rate was increased from 6.52mL/min/gcat to 19.57mL/min/gcat, the 2, 5-dichlorotoluene conversion was gradually decreased from 59.14% to 45.73%, and the selectivity of 2, 6-dichlorotoluene, 2, 4-dichlorotoluene, and dichlorotoluene increased with the increase in carrier gas flow rate. It was found that the progress of the isomerization reaction was more favorable when the carrier gas flow rate was higher, and the occurrence of side reactions was suppressed, thereby producing more dichlorotoluene isomers, but too high a carrier gas flow rate also caused a significant decrease in the catalytic activity of the catalyst.
When the carrier gas N 2 The catalyst had good catalytic activity at a flow rate of 6.52 mL/min/gcat. At this time, the conversion of 2, 5-dichlorotoluene was 59.14%, the selectivity for 2, 6-dichlorotoluene was 17.91%, and the selectivity for 2, 4-dichlorotoluene was 14.15%.
TABLE 6 influence of carrier gas flow rate on feedstock conversion and product selectivity
Claims (10)
1. A 2, 5-dichlorotoluene isomerization catalyst characterized by: the carrier of the catalyst is a hierarchical pore hydrogen type molecular sieve, the active component is zirconia, the cocatalyst is alkaline earth metal oxide, the total loading of the zirconia and the alkaline earth metal oxide is 1-5wt%, and the molar ratio of the zirconia to the alkaline earth metal is 10:0-0:10; the hierarchical pore hydrogen type molecular sieve is obtained by modifying a hydrogen type molecular sieve with an organic acid source.
2. The 2, 5-dichlorotoluene isomerization catalyst of claim 1, characterized in that: the hierarchical pore hydrogen type molecular sieve is prepared by the following method: immersing hydrogen molecular sieve in organic acid aqueous solution, reacting for 1-3 h at 70-90 ℃, filtering, washing the obtained solid with deionized water to neutrality, drying at 100-120 ℃, and roasting at 550 ℃ for 2-4 h to obtain the hierarchical pore hydrogen molecular sieve.
3. The 2, 5-dichlorotoluene isomerization catalyst of claim 2, characterized in that: the hydrogen type molecular sieve is H beta molecular sieve.
4. The 2, 5-dichlorotoluene isomerization catalyst of claim 2, characterized in that: the concentration of the organic acid aqueous solution of the hydrogen-type molecular sieve which is the H beta molecular sieve is 5-40 wt%, preferably 15wt%; the organic acid is any one of acetic acid, citric acid and oxalic acid, preferably oxalic acid.
5. The 2, 5-dichlorotoluene isomerization catalyst of claim 1, characterized in that: the total loading of zirconia and alkaline earth metal oxide was 3wt%; the molar ratio of zirconium to alkaline earth metal is 7:3 to 3:7, preferably 7:3 to 5:5, most preferably 7:3.
6. The 2, 5-dichlorotoluene isomerization catalyst of claim 1, characterized in that: the alkaline earth metal is Ca; the alkaline earth metal oxide is CaO.
7. A process for preparing the 2, 5-dichlorotoluene isomerization catalyst of claim 1, characterized by: the method comprises the following steps:
immersing a hydrogen type molecular sieve in an organic acid aqueous solution, reacting for 1-3 hours at the temperature of 70-90 ℃, filtering, washing the obtained solid to be neutral by using ionized water, drying at the temperature of 100-120 ℃, and roasting for 2-4 hours at the temperature of 550 ℃ to obtain the multi-stage pore hydrogen type molecular sieve;
step (2), zr (NO) 3 ) 4 ·5H 2 O and alkaline earth metal nitrate are dissolved in deionized water to obtain a mixed solution; mixing the mixed solution with a hierarchical pore hydrogen molecular sieve, soaking for 12-24 hours, filtering, drying the solid at the temperature of 110-120 ℃, and roasting for 3-5 hours at the temperature of 450-550 ℃ to obtain the 2, 5-dichlorotoluene isomerization catalyst.
8. A method for preparing 2, 4-dichlorotoluene and 2, 6-dichlorotoluene by catalytic isomerization of 2, 5-dichlorotoluene is characterized by comprising the following steps: comprising the following steps: takes 2, 5-dichlorotoluene as raw material and N 2 2, 5-dichlorotoluene isomerization catalyst as claimed in claim 1 as carrier gas, the mass space velocity of the raw material is 0.3-1.0 hr -1 The flow rate of the carrier gas is 6.5-20 mL/min/gcat, and the 2, 5-dichlorotoluene is subjected to isomerization reaction at the reaction temperature of 330-370 ℃ to produce 2, 4-dichlorotoluene and 2, 6-dichlorotoluene.
9. The process for preparing 2, 4-dichlorotoluene and 2, 6-dichlorotoluene by catalytic isomerization of 2, 5-dichlorotoluene according to claim 8, wherein: the reaction temperature is 340-360 ℃, preferably 350 ℃.
10. The process for preparing 2, 4-dichlorotoluene and 2, 6-dichlorotoluene by catalytic isomerization of 2, 5-dichlorotoluene according to claim 8, wherein: the mass airspeed of the raw materials is 0.4 to 0.8hr -1 Preferably 0.4hr -1 The method comprises the steps of carrying out a first treatment on the surface of the The flow rate of the carrier gas is 6.5-7 mL/min/gcat.
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