CN103041845A - Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition - Google Patents
Catalyst composition containing modified ZSM-11 zeolite and application of catalyst composition Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a catalyst composition containing modified ZSM-11 zeolite and an application of the catalyst composition. The catalyst composition comprises the following components of: 30-85 percent of ZSM-11 zeolite, 10-60 percent of binding agent, 0.1-10 percent of alkali metal oxide, 1-20 percent of ZSM-11 zeolite modified additive SiO2 and 1-20 percent of ZSM-11 zeolite modified additive alkali metal oxide. The catalyst composition disclosed by the invention is used in a methylbenzene alkylation process for synthesizing p-methyl methylbenzene from methylbenzene and ethylene and is favorable in catalytic reaction effect.
Description
Technical field
It is synthetic to the application in the methyl-ethyl benzene at toluene and ethene to the present invention relates to a kind of carbon monoxide-olefin polymeric and the application thereof that contains modified ZSM-5-11 zeolite, particularly this catalyst.
Background technology
P-methylstyrene can be obtained to the methyl-ethyl benzene dehydrogenation, after polymerization, the polymethylstyrene novel plastic can be produced.This polymer is at proportion, heat resistance, and the aspects such as transparency and shrinkage factor all are better than existing polystyrene plastics.In addition p-methylstyrene can with other monomer copolymerization, can improve heat resistance and the anti-flammability of some polymer, can be used in a large number engineering plastics, the manufacturing of the aspects such as phthalic resin coating, thereby in widespread attention.Also do not obtain for a long time the satisfactory method to methyl-ethyl benzene of high concentration, obtain the product of contraposition, a kind of well behaved shape-selective catalyst must be arranged, acid site intensity is suitable in pore size, grain size and the hole of requirement zeolite catalyst, and the acidity of outer surface is inhibited, might make the alkylation of toluene reaction break the thermodynamical equilibrium CONCENTRATION DISTRIBUTION of contraposition methyl-ethyl benzene, a position methyl-ethyl benzene, ortho position methyl-ethyl benzene product, mainly generate the contraposition methyl-ethyl benzene.Catalytic theory infers that the ZSM-5 molecular sieve think through chemical modification can make toluene and ethene vapor phase alkylation break through the restriction of thermodynamical equilibrium, can obtain 90% above concentration to methyl-ethyl benzene, and basically do not generate neighbour, a position methyl-ethyl benzene.In recent years, the research of this problem has caused the broad interest of each company and scientific research institution, and obtained certain progress, if can obtain further success, to produce dramatic change to the production technology to methyl-ethyl benzene, to energy savings, simplified apparatus, reduce production costs the very important meaning of having increased economic efficiency.
US5698756 uses methyl-silicone oil polymer (Dow-550) that the HZSM-5 molecular sieve of Si/Al=26 is carried out modification, the silicone oil polymer of each load 7.8%, and modification is 4 times altogether.Then in sodium nitrate solution the exchange three times, under 200 ℃, carry out drying again and catalyst.The evaluating catalyst condition is: 450 ℃ of temperature, toluene air speed 5 h
-1, benzene alkene is than 4, stagnation pressure 0.7MPa; Be to have obtained overall selectivity to methyl-ethyl benzene in 15.45% the situation greater than 77% effect in toluene conversion, but also have the methyl-ethyl benzene product at a certain amount of position and ortho position.
CN1103607A provides ethene and toluene reaction in a kind of catalytic cracked dry gas to produce shape selective catalysis agent to methyl-ethyl benzene.The agent of this kind shape selective catalysis is a kind of Pentasil type catalyst that contains rare earth, and select suitable chemical modifier to carry out modification: molecular sieve is carried out the dipping modifications such as aluminium and magnesium, the amount of its oxide modifier is not less than 0.25%.With modified catalyst at 350 ℃ ~ 420 ℃ of temperature, mass space velocity 0.3 ~ 0.5 h
-1, benzene alkene is checked and rated catalyst under the reaction condition of reaction pressure 0.1 ~ 1MPa than 4 ~ 6, can obtain conversion of ethylene more than 85% and 90% above selective to methyl-ethyl benzene.
Above document has all promoted the para-selectivity of product to methyl-ethyl benzene preferably, but the toluene conversion of product overall selectivity is still lower, can't satisfy the demand of actual production, thereby has limited its industrial applications.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of carbon monoxide-olefin polymeric that contains modified ZSM-5-11 zeolite and synthetic to the application in the methyl-ethyl benzene at toluene and ethene, it is not high to have solved in the prior art toluene conversion, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
The present invention contains the carbon monoxide-olefin polymeric of modified ZSM-5-11 zeolite, in catalyst weight percentage, has following composition: ZSM-11 zeolite 30% ~ 85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying additive alkali soil metal oxide 1% ~ 20%.
In the carbon monoxide-olefin polymeric of the present invention, modified additive silica and modified additive alkaline earth oxide load on the ZSM-11 zeolite, and order is elder generation's loaded modified additive alkali soil metal oxide, then loaded modified auxiliary agent silica.Loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, and with the ZSM-11 zeolite of silicon-containing organic compound processing alkaline earth oxide modification, then drying and roasting gets final product.
In the carbon monoxide-olefin polymeric of the present invention, ZSM-11 zeolite SiO
2/ Al
2O
3Mol ratio is 20 ~ 500, is preferably 30 ~ 200, more preferably 50 ~ 100, and by weight percentage, the content of ZSM-11 zeolite in catalyst is preferably 40% ~ 70%, and more preferably 50% ~ 60%.
In the carbon monoxide-olefin polymeric of the present invention, the content of ZSM-11 Zeolite modifying auxiliary agent silica is preferably 2% ~ 10%, and more preferably 3% ~ 8%.In the oxide that is selected from beryllium, magnesium, calcium, strontium, barium of ZSM-11 Zeolite modifying additive alkali soil metal oxide one or more are preferably beryllium or/and magnesium, more preferably magnesium; In catalyst weight percentage, the content of alkaline earth oxide is preferably 2% ~ 15%, and more preferably 5% ~ 12%.
In the carbon monoxide-olefin polymeric of the present invention, adhesive is aluminium oxide or silica, is preferably silica; By weight percentage, its content in catalyst is preferably 15% ~ 50%.
In the carbon monoxide-olefin polymeric of the present invention, alkali metal oxide be the oxide of sodium or/and the oxide of potassium, by weight percentage, its content in catalyst is preferably 0.5% ~ 5%, more preferably 1% ~ 3%.
The present invention contains modified ZSM-5-11 zeolite catalyst composition and is applied to toluene and ethylene selectivity alkylation and generates in the methyl-ethyl benzene course of reaction, the concrete technology condition can adjusted in a big way, for example, volume space velocity 0.5 h when hydrogen partial pressure 0.5MPa ~ 5.0MPa, 360 ℃ ~ 500 ℃ of reaction temperatures, toluene liquid
-1~ 10.0h
-1, toluene/ethylene molar ratio 1:1 ~ 10:1, hydrogen to oil volume ratio 200:1 ~ 1000:1(hydrogen and the volume ratio of toluene under standard conditions), optimum condition is: volume space velocity 2 h when hydrogen partial pressure 1MPa ~ 3MPa, 380 ℃ ~ 460 ℃ of reaction temperatures, toluene liquid
-1~ 5h
-1, toluene/ethylene molar ratio 3:1 ~ 5:1, hydrogen to oil volume ratio 300:1 ~ 500:1.
The present invention selects the ZSM-11 zeolite, after alkaline earth oxide modification and liquid-phase silicone deposition surface modification, adds suitable alkali metal compound, has prepared final catalyst.Catalyst of the present invention catalyzes and synthesizes methyl-ethyl benzene carrying out alkylation of toluene take ethene as raw material, when can obtain higher toluene conversion, can greatly suppress the side reactions such as transalkylation, has improved in the product selective to methyl-ethyl benzene.Can be used for synthetic production technology to methyl-ethyl benzene, the energy decrease is to operation easier and the energy consumption of the separative element of the product of methyl-ethyl benzene.It is not high that the carbon monoxide-olefin polymeric that contains modified ZSM-5-11 zeolite of the present invention has solved in the prior art toluene conversion, selectively lower to methyl-ethyl benzene, the problems such as the side reaction such as disproportionated reaction and isomerization reaction is serious, thus the effect of alkylation of toluene reaction improved.
The specific embodiment
The preparation method that the present invention contains modified ZSM-5-11 zeolite catalyst composition is as follows:
(1) alkaline earth metal compound is loaded on the ZSM-11 zeolite, through super-dry and roasting, obtain the ZSM-11 zeolite of alkaline earth oxide modification;
(2) with the ZSM-11 zeolite that contains the alkaline earth oxide modification that the solution impregnation step (1) that changes silicon compound makes, through super-dry and roasting, obtain the ZSM-11 zeolite of silicon-alkaline earth modification;
(3) modified ZSM-5-11 zeolite, adhesive, alkali compounds, extrusion aid and the abundant kneading of water that make of step (2) becomes plastic paste, and extruded moulding through super-dry and roasting, obtains catalyst of the present invention.
In the step (1), alkaline earth metal compound loads to the method on the ZSM-11 zeolite, can adopt ion-exchange, infusion process or kneading method, when wherein adopting ion-exchange or infusion process, the used alkaline including earth metal compound of solution of preparing the alkaline including earth metal compound is selected from one or more in the chloride of solubility, nitrate, the sulfate, be preferably and be selected from chloride and/or nitrate, more preferably chloride.When adopting kneading method, that the alkaline including earth metal compound is fully mixed with molecular sieve, the alkaline including earth metal compound is to be selected from oxide, chloride, nitrate, sulfate and the carbonate one or more, is preferably oxide and/or nitrate, more preferably nitrate.
The described modifier of step (2) is silicon-containing organic compound, is preferably the polyphenyl methylsiloxane, solvent can be can solvent modified dose organic matter or inorganic matter, be preferably organic hydrocarbon, such as n-hexane etc.;
The described adhesive of step (3) is for making the material of material forming, and for example aluminium oxide or silica are preferably silica, is the precursor of aluminium oxide or silica when using, such as aluminium hydroxide, Ludox, white carbon etc.Alkali compounds is that NaOH is or/and potassium hydroxide.Extrusion aid is the material that is conducive to extruded moulding, can be selected from graphite, starch, cellulose and the sesbania powder one or more, is preferably the sesbania powder, and by weight percentage, the amount of its adding is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
Drying condition described in step (1), (2) and (3) is normal temperature ~ 300 ℃ maintenance 1h ~ 48h, and step (1), step (2) and the described drying condition of step (3) can be identical, also can be different.The roasting condition of step (1), (2) and (3) is 400 ℃ ~ 800 ℃ and keeps 0.5h ~ 10.0h that step (1), step (2) and the described roasting condition of step (3) can be identical, also can be different.
Catalyst of the present invention is to adopt the medium-sized fixed bed reactors of 100ml to estimate, and loaded catalyst is 100ml, and appreciation condition is: volume space velocity 4.0h when hydrogen partial pressure 1.3MPa, 390 ℃ of reaction temperatures, toluene liquid
-1, toluene/ethylene molar ratio 4:1, hydrogen to oil volume ratio 400.Catalyst runs was carried out constituent analysis to tail gas and product liquid after 8 hours, calculated the selective of the conversion ratio of ethene and p-methyl-ethylbenzene, and concrete computational methods are as follows:
Further specify the preparation process of catalyst of the present invention below by embodiment, but invention should not be deemed limited among the following embodiment.
[embodiment 1](if followingly do not have special indicate, degree and form all take weight as benchmark)
The preparation process of carbon monoxide-olefin polymeric of the present invention is as follows:
(1) getting silica alumina ratio (silica/alumina molar ratio, lower with) is 80 ZSM-11 zeolite 300 grams, makes 450 milliliters of magnesium chloride solutions of counting 50 grams with content of magnesia.Solution and the ZSM-11 zeolite of above-mentioned magnesium chloride containing are fully mixed, after 110 ℃ of oven dry, the 500 ℃ of roastings in 4 hours, obtain consisting of of sample: magnesia/ZSM-11=1/6.
(2) the magnesium-modified ZSM-11 zeolite that makes with step (1) (350 gram), then flood with 500 milliliters of the hexane solutions take silica content as the polyphenyl methylsiloxane of 25 grams for preparing, leave standstill behind the dipping, thorough to solvent evaporates, 550 ℃ of lower roastings, obtain consisting of of sample: SiO after dry
2/ MgO/ZSM-11=0.5/1/6.
(3) modified ZSM-5 that makes with step (2)-11(400 gram), 117.5 gram white carbons (binding agent), 7.6 gram NaOH, 20 gram sesbania powder become plastic paste with the abundant kneading of an amount of water, extruded moulding (1.5 millimeters of diameters), through 120 ℃ of dryings of 8 hours and 550 ℃ of roastings of 3 hours, obtain catalyst of the present invention, it consists of: Na
2O/SiO
2/ MgO/ZSM-11/ binding agent=0.15/0.5/1/6/2.35(catalyst percentage consists of: Na
2O:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%), be numbered E-1, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment2]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of employed ZSM-11 zeolite is 38, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-2, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment3]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that employed magnesium-containing compound is magnesium nitrate, and employed binding agent is Ludox, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-3, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment4]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, the consisting of of the catalyst that obtains: Na
2O:0.5%, SiO
2: 3.5%, MgO:6%, ZSM-11:50%, binding agent: 40%, be numbered E-4, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment5]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, the consisting of of the catalyst that obtains: Na
2O:1%, SiO
2: 6%, MgO:9%, ZSM-11:70%, binding agent: 14%, be numbered E-5, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment6]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the silica alumina ratio of employed ZSM-11 zeolite is 120, and employed alkaline-earth metal is beryllium and magnesium, and catalyst form different, the consisting of of the catalyst that obtains: Na
2O:1%, SiO
2: 4%, BeO:1.8%, MgO:3.2%, ZSM-11:55%, binding agent: 35%, be numbered E-6, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment7]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the composition of catalyst is different, obtains consisting of of catalyst: Na
2O:5%, SiO
2: 4%, MgO:1%, ZSM-11:35%, binding agent: 55%, be numbered E-7, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment8]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, difference is that employed alkaline-earth metal component is magnesium nitrate, directly mix with molecular sieve, obtain modified ZSM-5-11 through oven dry and calcination process, the consisting of of the catalyst that obtains: Na
2O:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-8, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[embodiment9]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and difference is that the temperature and time of the drying that adopts in the preparation process and roasting is different, and actual conditions is: the treatment conditions of (1) step sample be 200 ℃ 2 hours, 380 ℃ 8 hours; (2) treatment conditions of step be 80 ℃ 16 hours, 580 ℃ 3 hours; (3) treatment conditions of step be 50 ℃ 48 hours, 490 ℃ 6 hours.Obtain catalyst of the present invention, it consists of: Na
2O:1.5%, SiO
2: 5%, MgO:10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-9, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[Comparative Examples 1]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is molecular sieve without alkali earth metal and siliceous deposits modification, and form different, the consisting of of the catalyst that obtains: Na
2O:2%, ZSM-11:60%, binding agent: 38%, be numbered C-1, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
[Comparative Examples 2]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is molecular sieve without the siliceous deposits modification, and form different, the consisting of of the catalyst that obtains: Na
2O:2%, MgO:10%, ZSM-11:60%, binding agent: 28%, be numbered C-2, its reaction result in the selective alkylation of toluene and ethene sees Table 1.
The evaluation result of table 1 different catalysts
| The embodiment numbering | Catalyst | Toluene conversion, % | P-methyl-ethylbenzene is selective, % |
| 1 | E-1 | 24.3 | 97.4 |
| 2 | E-2 | 24.7 | 97.1 |
| 3 | E-3 | 23.9 | 97.9 |
| 4 | E-4 | 23.3 | 98.2 |
| 5 | E-5 | 24.8 | 97.0 |
| 6 | E-6 | 23.1 | 98.6 |
| 7 | E-7 | 22.2 | 99.1 |
| 8 | E-8 | 24.3 | 97.5 |
| 9 | E-9 | 24.2 | 97.8 |
| The comparative example numbering | - | - | - |
| 1 | C-1 | 24.7 | 71.3 |
| 2 | C-2 | 24.4 | 76.9 |
Annotate: the evaluating catalyst process conditions are: volume space velocity 4.0h
-1, 390 ℃ of temperature, pressure 1.3MPa, toluene/ethylene ratio 4.0 (mol/mol), hydrogen to oil volume ratio 400,8 hours time.
Claims (10)
1. carbon monoxide-olefin polymeric that contains modified ZSM-5-11 zeolite, it is characterized in that with the carbon monoxide-olefin polymeric weight percent meter, has following composition: ZSM-11 zeolite 30% ~ 85%, adhesive 10%～60%, alkali metal oxide 0.1%～10%, ZSM-11 Zeolite modifying auxiliary agent silica 1 %～20%, ZSM-11 Zeolite modifying additive alkali soil metal oxide 1% ~ 20%.
2. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: modified additive silica and modified additive alkaline earth oxide load on the ZSM-11 zeolite, order is elder generation's loaded modified additive alkali soil metal oxide, then loaded modified auxiliary agent silica.
3. according to carbon monoxide-olefin polymeric claimed in claim 2, it is characterized in that: loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, with the ZSM-11 zeolite of silicon-containing organic compound processing alkaline earth oxide modification, then dry and roasting gets final product.
4. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: ZSM-11 zeolite SiO
2/ Al
2O
3Mol ratio is 20 ~ 500, and by weight percentage, the content of ZSM-11 zeolite in catalyst is 40% ~ 70%.
5. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: the content of ZSM-11 Zeolite modifying auxiliary agent silica is 2% ~ 10%.
6. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: one or more in the oxide that is selected from beryllium, magnesium, calcium, strontium, barium of ZSM-11 Zeolite modifying additive alkali soil metal oxide, in catalyst weight percentage, the content of alkaline earth oxide is 2% ~ 15%.
7. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: adhesive is aluminium oxide or silica, and by weight percentage, the content of adhesive in catalyst is 15% ~ 50%.
8. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: alkali metal oxide be the oxide of sodium or/and the oxide of potassium, by weight percentage, the content of alkali metal oxide in catalyst is 0.5% ~ 5%.
9. the described carbon monoxide-olefin polymeric of the arbitrary claim of claim 1 to 8 generates the application in the methyl-ethyl benzene course of reaction at toluene and ethylene selectivity alkylation.
10. according to application claimed in claim 9, it is characterized in that: it is that 0.5MPa ~ 5.0MPa, reaction temperature are 360 ℃ ~ 500 ℃, volume space velocity is 0.5 h during toluene liquid that toluene and ethylene selectivity alkylation generate methyl-ethyl benzene reaction hydrogen partial pressure
-1~ 10.0h
-1, toluene/ethylene molar ratio is 1:1 ~ 10:1, hydrogen to oil volume ratio is 200:1 ~ 1000:1.
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