CN103041846B - Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst - Google Patents
Alkylated catalyst containing modified ZSM-11 zeolite and application of alkylated catalyst Download PDFInfo
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Abstract
The invention discloses an alkylated catalyst containing modified ZSM-11 zeolite and an application of the alkylated catalyst. The alkylated catalyst comprises the following components in percentage by weight: 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 0.5-30 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
The present invention relates to a kind of alkylation catalyst and application thereof containing modified ZSM-5-11 zeolite, be especially in use in the synthetic form selected methylation catalyst to methyl-ethyl benzene of toluene and ethene.
Background technology
To methyl-ethyl benzene dehydrogenation, p-methylstyrene can be obtained, after polymerization, polymethylstyrene novel plastic can be produced.This polymer is at proportion, heat resistance, and the aspects such as transparency and shrinkage factor are all 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 in a large number for engineering plastics, the manufacture 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, must there is a kind of well behaved shape-selective catalyst, in pore size, grain size and the hole of requirement zeolite catalyst, acid site intensity is suitable, and the acidity of outer surface is inhibited, likely make 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 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 substantially do not generate neighbour, a position methyl-ethyl benzene.In recent years, the research of this problem causes the broad interest of Liao Ge company and scientific research institution, and obtained certain progress, if can obtain further success, production technology to methyl-ethyl benzene is produced to dramatic change, to saving the energy, simplified apparatus, reduce production costs, the very important meaning of having increased economic efficiency.
US5698756 is used methyl-silicone oil polymer (Dow-550) to carry out modification to the HZSM-5 molecular sieve of Si/Al=26, the silicone oil polymer of each load 7.8%, and modification is 4 times altogether.Then in sodium nitrate solution, exchange three times, then at 200 ℃, be dried and catalyst.Evaluating catalyst condition is: 450 ℃ of temperature, toluene air speed 5 h
-1, benzene alkene is than 4, stagnation pressure 0.7MPa; In the situation that toluene conversion is 15.45%, has obtained the overall selectivity of methyl-ethyl benzene has been greater than to 77% effect, but also had 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 the shape selective catalysis agent to methyl-ethyl benzene.This kind of shape selective catalysis agent is a kind of Pentasil type catalyst containing rare earth, selects suitable chemical modifier to carry out modification: molecular sieve is carried out to the dipping modifications such as aluminium and magnesium, the amount of its oxide modifier is not less than 0.25%.By modified catalyst at 350 ℃ ~ 420 ℃ of temperature, mass space velocity 0.3 ~ 0.5 h
-1, benzene alkene, than 4 ~ 6, is checked and rated catalyst under the reaction condition of reaction pressure 0.1 ~ 1MPa, can obtain more than more than 85% conversion of ethylene and 90% 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 meet 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 catalyst containing modified ZSM-5-11 zeolite and synthetic to the application in methyl-ethyl benzene at toluene and ethene, solved in prior art toluene conversion not high, 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 is containing the alkylation catalyst of modified ZSM-5-11 zeolite, in catalyst weight percentage, there is 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 auxiliary agent rare-earth oxide 0.5% ~ 30%.
In carbon monoxide-olefin polymeric of the present invention, modified additive silica and modified additive rare-earth oxide load on ZSM-11 zeolite, and order is first loaded modified auxiliary agent rare-earth oxide, then loaded modified auxiliary agent silica.Loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, processes the ZSM-11 zeolite of rare-earth oxide modification, then drying and roasting with silicon-containing organic compound.
In catalyst 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 catalyst of the present invention, the content of ZSM-11 Zeolite modifying auxiliary agent silica is preferably 2% ~ 10%, and more preferably 3% ~ 8%.The thulium of ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide is selected from one or more in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium, is preferably lanthanum or/and cerium; In catalyst weight percentage, the content of rare-earth oxide is preferably 1% ~ 15%, and more preferably 2% ~ 10%.
In 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 carbon monoxide-olefin polymeric of the present invention, the oxide that alkali metal oxide is sodium is or/and the oxide of potassium, and by weight percentage, its content in catalyst is preferably 0.5% ~ 5%, and more preferably 1% ~ 3%.
The present invention is applied to toluene containing modified ZSM-5-11 zeolite catalyst composition and ethylene selectivity alkylation generates in methyl-ethyl benzene course of reaction, 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 ZSM-11 zeolite, after rare-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 as raw material carries out alkylation of toluene take ethene, when can obtain higher toluene conversion, can greatly suppress the side reactions such as transalkylation, has improved in product selective to methyl-ethyl benzene.Can be used for the synthetic production technology to methyl-ethyl benzene, can significantly reduce the operation easier of the separative element of the product of methyl-ethyl benzene and energy consumption.It is not high that carbon monoxide-olefin polymeric containing modified ZSM-5-11 zeolite of the present invention has solved in 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 process of catalyst of the present invention mainly comprises following steps:
(1) rare earth compound is loaded on ZSM-11 zeolite, through super-dry and roasting, obtain the ZSM-11 zeolite of rare-earth oxide modification;
(2) the ZSM-11 zeolite of the rare-earth oxide modification making by the solution impregnation step (1) containing changing silicon compound, through super-dry and roasting, obtains silicon-rare earth modified ZSM-11 zeolite;
(3) the abundant kneading of modified ZSM-5-11 zeolite, adhesive, alkali compounds, extrusion aid and water that step (2) makes becomes plastic paste, and extruded moulding, through super-dry and roasting, obtains catalyst of the present invention.
In step (1), rare earth compound loads on molecular sieve can adopt ion-exchange, infusion process or kneading method, while wherein adopting ion-exchange or infusion process, the solution compounds containing rare earth used of preparation compounds containing rare earth are selected from chloride and/or nitrate, more preferably nitrate.While adopting kneading method, be that compounds containing rare earth are fully mixed with molecular sieve, compounds containing rare earth are to be selected from one or more in oxide, chloride, nitrate, sulfate and carbonate, are preferably oxide and/or nitrate, more preferably nitrate.
The described modifier of step (2) is silicon-containing organic compound, is preferably 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, be preferably silica, is the precursor of aluminium oxide or silica, as aluminium hydroxide, Ludox, white carbon etc. during use.Described alkali compounds is that NaOH is or/and potassium hydroxide.Described extrusion aid is the material that is conducive to extruded moulding, can be selected from one or more in graphite, starch, cellulose and sesbania powder, is preferably sesbania powder, and by weight percentage, its amount adding is 0.5% ~ 10% of carrier butt, is preferably 1% ~ 5%.
Drying condition described in step (1), (2) and (3) is that normal temperature ~ 300 ℃ keep 1h ~ 48h, and the described drying condition of step (1), step (2) and step (3) can be identical, also can be different.The roasting condition of step (1), (2) and (3) is 400 ℃ ~ 800 ℃ maintenance 0.5h ~ 10.0h, and the described roasting condition of step (1), step (2) and 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 evaluate, 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, 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:
×100%
×100%
Below by embodiment, further illustrate the preparation process of catalyst of the present invention, but invention should not be deemed limited in following embodiment.
[embodiment 1](if there is no below special indicating, degree is all weight percentage)
The preparation process of a kind of catalyst of the present invention is as follows:
(1) getting silica alumina ratio (silica/alumina molar ratio, lower with) is 300 grams, 80 ZSM-11 zeolite, makes 450 milliliters and take the lanthanum nitrate hexahydrate that lanthana content is 50 grams.Above-mentioned solution and ZSM-11 zeolite containing lanthanum nitrate fully mixed, after 110 ℃ of oven dry, 500 ℃ of roastings in 4 hours, obtain consisting of of sample: lanthana/ZSM-11=1/6.
(2) ZSM-11(350 gram of the lanthana modification making by (1) step), then with 500 milliliters of the hexane solutions of the polyphenyl methylsiloxane that silica content is 25 grams of take that prepare, flood, standing after dipping, thorough to solvent evaporates, roasting at 550 ℃ after dry, obtains consisting of of sample: SiO
2/ La
2o
3/ ZSM-11=0.5/1/6.
(3) modified ZSM-5-11(400 gram making by (2) step), 117.5 grams of white carbons (binding agent), 7.6 grams of NaOH, 20 grams of sesbania powder become plastic paste with the appropriate abundant kneading of water, extruded moulding (1.5 millimeters of diameters), through 120 ℃ of dry and 550 ℃ of roastings of 3 hours of 8 hours, obtain catalyst of the present invention, it consists of: Na
2o/SiO
2/ La
2o
3/ ZSM-11/ binding agent=0.15/0.5/1/6/2.35(catalyst percentage consists of: Na
2o:1.5%, SiO
2: 5%, La
2o
3: 10%, ZSM-11:60%, binding agent: 23.5%), be numbered E-1, its reaction result in the selective alkylation of toluene and ethene is in 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 used ZSM-11 zeolite is 38, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, La
2o
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-2, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
[embodiment3]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and it is lanthanum chloride containing lanthanum compound that difference is used, and the binding agent using is Ludox, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, La
2o
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-3, its reaction result in the selective alkylation of toluene and ethene is in 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 obtaining: Na
2o:0.5%, SiO
2: 3.5%, La
2o
3: 6%, ZSM-11:50%, binding agent: 40%, be numbered E-4, its reaction result in the selective alkylation of toluene and ethene is in 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 obtaining: Na
2o:1%, SiO
2: 6%, La
2o
3: 9%, ZSM-11:70%, binding agent: 14%, be numbered E-5, its reaction result in the selective alkylation of toluene and ethene is in 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 used ZSM-11 zeolite is 120, and the rare earth metal using is lanthanum and cerium, and catalyst form different, the consisting of of the catalyst obtaining: Na
2o:1%, SiO
2: 4%, La
2o
3: 1.8%, Ce
2o
3: 3.2%, ZSM-11:55%, binding agent: 35%, be numbered E-6, its reaction result in the selective alkylation of toluene and ethene is in 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%, La
2o
3: 1%, ZSM-11:35%, binding agent: 55%, be numbered E-7, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
[embodiment8]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, difference is that used thulium compound is lanthanum chloride, directly mix with molecular sieve, through oven dry and calcination process obtains modified ZSM-5-11 zeolite, the consisting of of the catalyst obtaining: Na
2o:1.5%, SiO
2: 5%, La
2o
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-8, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
[embodiment9]
The preparation method of a kind of catalyst of the present invention is with embodiment 1, and it is dry different with the temperature and time of roasting that difference is to adopt in preparation process, 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%, La
2o
3: 10%, ZSM-11:60%, binding agent: 23.5%, be numbered E-9, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
[comparative example 1]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is that molecular sieve is without thulium and siliceous deposits modification, and form different, the consisting of of the catalyst obtaining: Na
2o:2%, ZSM-11:60%, binding agent: 38%, be numbered C-1, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
[comparative example 2]
A kind of comparative catalyst's of the present invention preparation method is with embodiment 1, and difference is that molecular sieve is without siliceous deposits modification, and form different, the consisting of of the catalyst obtaining: Na
2o:2%, La
2o
3: 10%, ZSM-11:60%, binding agent: 28%, be numbered C-2, its reaction result in the selective alkylation of toluene and ethene is in Table 1.
the evaluation result of table 1 different catalysts
| Embodiment numbering | Catalyst | Toluene conversion, % | P-methyl-ethylbenzene is selective, % |
| 1 | E-1 | 24.1 | 97.8 |
| 2 | E-2 | 24.2 | 97.5 |
| 3 | E-3 | 23.7 | 97.7 |
| 4 | E-4 | 23.6 | 98.3 |
| 5 | E-5 | 24.2 | 97.4 |
| 6 | E-6 | 23.4 | 98.2 |
| 7 | E-7 | 22.5 | 98.8 |
| 8 | E-8 | 24.0 | 98.1 |
| 9 | E-9 | 24.3 | 98.6 |
| Comparative example numbering | - | - | - |
| 1 | C-1 | 24.2 | 78.6 |
| 2 | C-2 | 24.6 | 87.0 |
Note: evaluating catalyst process conditions are: volume of toluene air speed 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.
From the result of table 1, show, the present invention selects ZSM-11 zeolite, after liquid-phase silicone deposition surface modification, added the catalyst making after rare-earth oxide, as carrying out alkylation of toluene, raw material catalyzes and synthesizes methyl-ethyl benzene take ethene, when can obtain higher toluene conversion, can greatly suppress the side reactions such as transalkylation, improve in product selective to methyl-ethyl benzene.Can be used for the synthetic production technology to methyl-ethyl benzene, can significantly reduce the operation easier of the separative element of the product of methyl-ethyl benzene and energy consumption.
Claims (10)
1. the alkylation catalyst containing modified ZSM-5-11 zeolite, it is characterized in that in catalyst weight percentage, there is 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 auxiliary agent rare-earth oxide 0.5%～30%;
Described ZSM-11 Zeolite modifying auxiliary agent silica and ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide load on ZSM-11 zeolite, and order is first loaded modified auxiliary agent rare-earth oxide, then loaded modified auxiliary agent silica.
2. according to catalyst claimed in claim 1, it is characterized in that: loaded modified auxiliary agent silica adopts liquid-phase silicone deposition processes method, with silicon-containing organic compound, process the ZSM-11 zeolite of rare-earth oxide modification, then drying and roasting.
3. according to catalyst claimed in claim 1, it is characterized in that: the SiO of ZSM-11 zeolite
2/ Al
2o
3mol ratio is 20～500, by weight percentage, and the content 40%～70% of ZSM-11 zeolite in catalyst.
4. according to catalyst claimed in claim 1, it is characterized in that: the content of ZSM-11 Zeolite modifying auxiliary agent silica is 2%～10%.
5. according to catalyst claimed in claim 1, it is characterized in that: the thulium of ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide is selected from one or more in lanthanum, cerium, praseodymium, rubidium, promethium, samarium, europium, dysprosium, gadolinium, bait, thulium, ytterbium and lutetium; In catalyst weight percentage, the content of rare-earth oxide is 1%～15%.
6. according to catalyst claimed in claim 5, it is characterized in that: the thulium of ZSM-11 Zeolite modifying auxiliary agent rare-earth oxide is that lanthanum is or/and cerium.
7. according to catalyst claimed in claim 1, it is characterized in that: adhesive is aluminium oxide or silica, by weight percentage, the content of adhesive in catalyst is 15%～50%.
8. according to catalyst claimed in claim 1, it is characterized in that: the oxide that alkali metal oxide is sodium is or/and the oxide of potassium, and by weight percentage, the content of alkali metal oxide in catalyst is 0.5%～5%.
9. described in the arbitrary claim of claim 1 to 8, catalyst generates the application in 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 0.5h during toluene liquid that toluene and ethylene selectivity alkylation generate the hydrogen partial pressure that methyl-ethyl benzene is reacted
-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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| CN107754848B (en) * | 2016-08-23 | 2020-12-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing p-methyl ethyl benzene by shape-selective catalysis of carbon octaene |
| CN106669828A (en) * | 2016-11-28 | 2017-05-17 | 宣城市聚源精细化工有限公司 | Preparation method of catalyst applied to alkylation reaction of toluene and tertiary butanol |
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|---|---|---|---|---|
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN101940943A (en) * | 2010-09-28 | 2011-01-12 | 同济大学 | Shape-selective alkylation catalyst for synthesizing p-cymene with toluene and propylene as raw materials |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201717A (en) * | 1997-06-06 | 1998-12-16 | 中国石油化工总公司 | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene |
| CN101954293A (en) * | 2010-09-27 | 2011-01-26 | 同济大学 | Method for preparing catalyst for alkylation reaction of methylbenzene and ethylene for synthesizing paramethyl ethylbenzene |
| CN101940943A (en) * | 2010-09-28 | 2011-01-12 | 同济大学 | Shape-selective alkylation catalyst for synthesizing p-cymene with toluene and propylene as raw materials |
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