CN108043449A - A kind of preparation method of highly selective anti-carbon benzene alkylation catalyst - Google Patents
A kind of preparation method of highly selective anti-carbon benzene alkylation catalyst Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
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Abstract
The invention belongs to petrochemical catalyst technical field, a kind of preparation method of highly selective anti-carbon benzene alkylation catalyst.First：Select parent of the high silica alumina ratio MFI zeolite molecular sieves as catalyst；Second：It is mixed with acidifying silicone grease hydrolysate with high silica alumina ratio MFI zeolite molecular sieves, extruded moulding, then handles bar shaped molding with the aqueous solution of ammonium hexafluorosilicate；3rd：The bar shaped molding of the separation mother liquid disposal high silica alumina ratio MFI zeolite molecular sieves obtained during with hydrothermal crystallizing high silica alumina ratio MFI zeolite molecular sieves；4th, the bar shaped molding of the high silica alumina ratio MFI zeolite molecular sieves after mother liquid disposal is transformed by Hydrogen alkylation catalyst using ion-exchange.The mother liquor generated when the present invention is by hydrothermal synthesis high silica alumina ratio MFI zeolite molecular sieves is for the bar shaped catalyst after processing shaping, the useful component in mother liquor is not only recycled, the duct of catalyst has been dredged, alkylation catalyst has been also reduced and produces environmental pollution in chain entirely.
Description
Technical field
The invention belongs to petrochemical catalyst technical fields, are related to a kind of preparation method of benzene alkylation catalyst.
Background technology
Benzene and methanol, the vapor-phase alkylation of ethyl alcohol can be respectively used to synthesis dimethylbenzene and ethylbenzene, the former can be used for production pair
Dimethylbenzene, and then produce terephthalic acid (TPA)；The latter can be used for dehydrogenation to produce styrene, and then produce polystyrene etc..Because have
Water generates, so benzene and methanol, benzene and ethanol alkylation can only carry out under high temperature and the reaction condition of gas phase, so face with
Lower common problem：(1) the mutual isomerization side reaction between dimethylbenzene and ethylbenzene how is reduced.That is, in benzene and methanol
In alkylation, further isomerization reaction of the purpose product dimethylbenzene to by-product ethylbenzene is reduced to the greatest extent.The side reaction is given birth to
Into ethylbenzene by-product can influence the efficiency of dimethylbenzene isomerization workshop section in p-X production procedures；And in benzene and ethanol alkylation
In, then to reduce further isomerization reaction of the purpose product ethylbenzene to by-product dimethylbenzene to the greatest extent.Because the side reaction is given birth to
Into a small amount of xylene impurities can influence the purity of styrene downstream product, limit its application range；(2) how catalyst is slowed down
Carbon distribution deactivation rate under the conditions of low benzene alcohol ratio, to enable catalyst long-term operation under relatively mild conditions.
Have the preparation method of the benzene alkylation catalyst disclosed by patent, do not well solve ethylbenzene and dimethylbenzene
Isomerization side reaction problem.In addition, the benzene alkylation catalyst having disclosed by patent can only all be run under high benzene alcohol ratio
Just there is preferable activity stability.But using high benzene alcohol ratio benzene internal circulating load will be caused to increase, the energy consumption for making industrialized unit is big
Amplitude increases, and is unfavorable for commercial Application.For example,
One kind that Chinese invention patent (application number 201010200020.5) discloses is for ethyl alcohol and benzene vapor-phase alkylation system
The method for preparing catalyst of ethylbenzene, technical characteristic are to be modified silica alumina ratio SiO with lanthanum nitrate hexahydrate2/Al2O3For 30~
400th, crystal grain diameter is 5~350 nanometers of Hydrogen ZSM-5 molecular sieve, then by modifier and binding agent aluminium oxide or titanium dioxide
Silicon extruded moulding finally carries out high-temperature vapor processing and phosphoric acid modification to the catalyst of extruded moulding again.It makes in aforementioned manners
Standby catalyst when carrying out benzene and ethyl alcohol vapor phase alkylation on the pressurization static bed reaction unit of fixation continuously flowed,
Reaction temperature is 390 DEG C, reaction pressure 1.2MPa, when ethyl alcohol weight space velocity is 0.8 small-1, benzene/ethyl alcohol molar ratio is 6.5
Under the conditions of, xylene content is up to 800ppm in product ethylbenzene.
One kind that Chinese invention patent (application number 201110192629.7) discloses is for ethyl alcohol and benzene vapor-phase alkylation system
The method for preparing catalyst of ethylbenzene, technical characteristic are that its technical characteristic is to be modified silica alumina ratio with alkaline-earth metal salt solution
SiO2/Al2O3For the Hydrogen ZSM-5 molecular sieve that 30~400, crystal grain diameter is 5~350 nanometers, then by modifier and binding agent
Aluminium oxide or silica extruded moulding finally carry out high-temperature vapor processing to the catalyst of extruded moulding again and phosphoric acid change
Property.The catalyst prepared in aforementioned manners carries out benzene and ethyl alcohol gas phase on the pressurization static bed reaction unit of fixation continuously flowed
It it is 390 DEG C, reaction pressure 1.2MPa in reaction temperature, when ethyl alcohol weight space velocity is 0.8 small during alkylated reaction-1, benzene/second
Under conditions of alcohol molar ratio is 6.5, xylene content is up to 600ppm in product ethylbenzene.
One kind that Chinese invention patent (application number 201110367348.0) discloses is for ethyl alcohol and benzene vapor-phase alkylation system
The method for preparing catalyst of ethylbenzene, technical characteristic are the silica alumina ratio SiO2/Al2O3 of rare-earth salt solution modified no-adhesive
For the Hydrogen ZSM-5 molecular sieve that 30~400, crystal grain diameter is 5~350 nanometers, then again to passing through rare earth modified soap-free emulsion polymeization
Agent catalyst is modified using high-temperature vapor processing and phosphoric acid solution.The catalyst prepared in aforementioned manners is consolidated what is continuously flowed
It is 390 DEG C in reaction temperature when carrying out benzene with ethyl alcohol vapor phase alkylation on fixed pressurization static bed reaction unit, reaction pressure
For 1.2MPa, ethyl alcohol weight space velocity for 0.8 it is small when-1, under conditions of benzene/ethyl alcohol molar ratio is 6.5, dimethylbenzene contains in product ethylbenzene
Amount is up to 800ppm.
The content of the invention
The present invention provides a kind of new benzene and methanol, the preparation method of ethanol alkylation catalyst.This method can be effective
Inhibit the mutual isomerization reaction between ethylbenzene and dimethylbenzene, and effectively slow down the decay of activity rate of catalyst, extension is urged
The one way cycle of operation of agent.We by basic research find, benzene and methanol alkylation production dimethylbenzene when, dimethylbenzene to
The isomerization reaction of ethylbenzene and benzene and ethanol alkylation production ethylbenzene when, isomerization reaction of the ethylbenzene to dimethylbenzene is all
Secondary side reaction.It reduces the acid activated centre density of catalyst and is arranged with dredging catalyst duct two and developed simultaneously, be to reduce these
The most effectual way of secondary side reaction Probability.In this regard, the specific aim scheme that the present invention takes is, on the one hand using high sial
The MFI zeolite molecular sieves of ratio reduce the acid activated centre density of catalyst.On the other hand by using acidifying silicon ester hydrolysis
Object with molecular sieve extruded moulding and then with synthesis of molecular sieve when the particulate matter of separation mother liquid disposal extruded moulding that generates dredge
The duct of logical catalyst.We also found by basic research, is easy in the high silica alumina ratio MFI zeolite molecular sieves of hydrothermal crystallizing
There is substantial amounts of oxygen-octahedron shortcoming position i.e. hydroxyl nest.A large amount of presence of hydroxyl nest are unfavorable for benzene and methanol, benzene and ethyl alcohol
Vapor phase alkylation.Main problem is that hydroxyl nest has hydrophily, can be enriched with alcohols, and the carbon distribution for significantly speeding up catalyst loses
It is living, so as to shorten the one way cycle of operation of catalyst.In this regard, the specific aim scheme that the present invention takes is, at separation mother liquor
First silicon is mended before reason to the making choice property of catalyst of extruded moulding with the neutral solution of ammonium hexafluorosilicate to handle.
Technical scheme：
A kind of preparation method of highly selective anti-carbon benzene alkylation catalyst, step are as follows：
The first step：Select parent of the high silica alumina ratio MFI zeolite molecular sieves as catalyst.
The silica alumina ratio (SiO2/Al2O3) of MFI zeolite molecular sieves is improved, the acid activated centre that can reduce catalyst is close
Degree, and then the chance that the purpose product ethylbenzene (or dimethylbenzene) for reducing primary first-order equation generation meets again with acid activated centre,
Reduce probability of the above-mentioned purpose product to by-product dimethylbenzene (or ethylbenzene) isomerization.Described high silica alumina ratio MFI zeolite molecules
Sieve refers to the MFI molecular sieves that silica alumina ratio reaches more than 400.Especially silica alumina ratio reaches the MFI zeolite molecular sieves of 500-1000.
MFI zeolite molecular sieve of the silica alumina ratio less than 400 also has the catalytic action of benzene alkylation reaction.It is moreover, low herein
It can also be observed that the phenomenon that isomerization side reaction is reduced with the raising of molecular sieve silica alumina ratio in the range of silica alumina ratio.But it compares
Under, in the range of high silica alumina ratio of the presently claimed invention, the degree that isomerization side reaction occurs is lower.
The engineer for being familiar with this field will recognize that sometimes through high-temperature vapor processing to remove low silica-alumina ratio zeolite molecules
A part of framework aluminum on sieve.This way objectively can also improve silica alumina ratio and reduce acid activated centre density.But it uses
This method, which improves silica alumina ratio and then reduces activated centre density, can destroy the integrality of zeolitic frameworks, be caused on zeolitic frameworks
Many hydroxyl nest shortcomings.There is specialised literature [280 (2011) 196-205 of Journal of Catalysis] to point out, high silicon
Hydroxyl nest on MFI skeletons can increase the speed of catalyst carbon deposition inactivation.Therefore, the present invention is not passivated dealuminzation method using water vapour
High silica alumina ratio MFI molecular sieves are prepared, but use the direct synthesizing high-silicon aluminium of hydro-thermal method than MFI molecular sieve.
For the engineer of this field, the high silica alumina ratio MFI zeolite molecular sieves described in the present invention are readily available, can
It is obtained with the method hydrothermal synthesis disclosed according to following patent：A kind of Chinese invention patent ZL200510200328.9 (high sial
The synthetic method of the small crystal grain ZSM-5 zeolite molecular sieve of ratio), a kind of Chinese invention patent ZL201110364516.0 (ZSM-5 boilings
The synthetic method of stone), Chinese invention patent ZL2013100810 07.6 (a kind of preparation method of high dispersive zeolite molecular sieve).
Second step：With the hydrolysate of silicone grease and high silica alumina ratio MFI zeolite molecular sieve extruded mouldings is acidified, then with hexafluoro silicon
The aqueous solution processing extruded moulding object of sour ammonium.
Described acidifying silicone grease hydrolysate refers to the hydrolysate of ethyl orthosilicate in acid condition through negative pressure except after alcohol
Obtained jello.Molecular sieve molded in order to be conducive to, silicone grease hydrolysising condition is preferred：The molar ratio of ethyl orthosilicate and water is
0.5-10, hydrolysis pH value ＜ 7.0, hydrolysis temperature are room temperature, hydrolysis time 0.5-100h.In described acidifying silicone grease hydrolysate
Solid content is controlled in the range of 20-30wt.%.
When carrying out extruded moulding using above-mentioned acidifying silicone grease hydrolysate and high silica alumina ratio MFI zeolite molecular sieves powder, to control
Molecular sieve content in molding processed is in more than 60wt%.With above-mentioned acidifying silicone grease hydrolysate and high silica alumina ratio MFI zeolite molecules
Sieve powder can add a small amount of atoleine and sesbania powder auxiliary agent when preparing extrusion material.Wherein, the addition of sesbania powder is bar shaped
The 3-5wt.% of catalyst butt weight, the addition of atoleine are the 1-3wt.% of bar shaped catalyst butt weight.Wherein,
The optional density of atoleine is 0.835-855, and recovered (distilled) temperature is 300 DEG C of industrial goods.Extruded moulding object can be according to Normal practice
It is dried and calcination process.
It is clear that with the hydrolysate of other estersil such as methyl silicate etc. of acidifying and high silica alumina ratio MFI zeolite molecular sieves
Extruded moulding can also reach above-mentioned purpose.The estersil hydrolysate of acidifying is even substituted with raw materials such as industry silicasol and white carbons
Also molding can be made to reach the effect in dredging duct in mother liquid disposal.But during with industry silicasol and white carbon, extrusion into
The catalyst granules intensity of type is relatively poor, is unfavorable for catalyst and is used in fixed bed.On the other hand, boehmite (has
Effect ingredient alundum (Al2O3)) it is that be in daily use molecular sieve molded uses binding agent.Boehmite is in molding by sizing roasting
Burning is usually transformed into γ type alundum (Al2O3)s.Molecular sieve pore passage caused by this type alundum (Al2O3) as γ is blocked in alkaline item
It is difficult to dissolve dredging under part, and the aluminium species being dissolved down can generate the MFI crystals of low silica-alumina ratio in recrystallization process, no
Beneficial to the acid activated centre density for reducing catalyst.
Mending the condition of silicon processing to making choice property of extruded moulding catalyst with the neutral aqueous solution of ammonium hexafluorosilicate is：Place
80-200 DEG C of temperature of reason, preferably 90-170 DEG C；Liquid-solid ratio is 1-20, preferably 5-10；Ammonium hexafluorosilicate concentration of aqueous solution 0.01-
0.10M, preferably 0.03-0.05M；Solution ph is 6-7；Processing time is 0.5-100h, preferably 10-30h.It is worth mentioning
It is that the aqueous solution of ammonium hexafluorosilicate is highly acid (pH ＜ 5) in itself.Therefore, the aqueous solution of ammonium hexafluorosilicate is commonly used in
The dealumination complement silicon of molecular sieve.The purposes of this respect is recorded via many documents.But the purpose of present invention ammonium hexafluorosilicate
Only it is to mend silicon, does not lie in dealuminzation.For this purpose, the ammonium hexafluorosilicate solution ph used in the present invention is adjusted precisely to by basic species and connects
Weakly acidic pH, to eliminate the dealuminization of acid medium, here it is signified selectivity of the invention to mend silicon.Described alkaline matter
Can be the organic bases such as the inorganic bases such as sodium hydroxide or ammonium hydroxide.It needs to be emphasized that ammonium hexafluorosilicate is molten
The pH value of liquid cannot excessively high (such as ＞ 8), otherwise can cause hexafluorosilicic acid root anion hydrolysis generation Ludox.
3rd step：The separation mother liquid disposal high silica alumina ratio MFI obtained during with hydrothermal crystallizing high silica alumina ratio MFI zeolite molecular sieves
The molding of zeolite molecular sieve.
MFI zeolites point after the separation mother liquid disposal shaping obtained during with hydrothermal crystallizing high silica alumina ratio MFI zeolite molecular sieves
Son sieve, is to dredge the duct of preformed catalyst.And it is carried out with acidifying silicone grease hydrolysate with high silica alumina ratio MFI zeolite molecular sieves
Extruded moulding, the then effect that catalyst duct is dredged during mother liquid disposal are best.
The separation mother liquor of hydrothermal crystallizing high silica alumina ratio MFI zeolite molecular sieves is synthesizing high-silicon aluminium than MFI zeolite molecules riddlers
The waste liquid of section discharge, wherein about containing the template of inventory 10-20% when being equivalent to Zeolite synthesis, 5-10% silicon,
Aluminium active specy, and in alkaline (usual pH ＞ 10).This hydrothermal crystallizing mother liquor seriously endangers ring usually as discharging of waste liquid
Border.Being recycled back Zeolite synthesis workshop section recycling then can usually cause molecular sieve quality unstable.The present invention uses it for
MFI zeolite molecular sieves duct after processing and dredging shaping, dexterously solves molecular sieve synthesis mother liquid emission problem and catalysis
Agent is modified problem.Its handle and dredging shaping after the principle in high silica alumina ratio MFI zeolite molecular sieves duct be：On the one hand using female
The alkaline medium of liquid promotes the dissolving for the unformed silicon matter that duct is caused to block in extruded moulding object；On the one hand using in mother liquor
It is high silica alumina ratio MFI zeolite molecular sieve skeletons that the template contained, which promotes dissolved matter crystallization,.Pass through above dissolution-crystallization process
Achieve the purpose that dredge molded molecular sieve duct.In the process, silicon, the aluminium active specy contained in mother liquor can also pass through participation
Crystallization process and largely consumed, and nitrogenous organic formwork agent is then substantially thoroughly consumed, and solves directly discharge mother liquor
Pollution problem, recycled useful component therein.
With the high silica alumina ratio MFI zeolite molecules after the hydrothermal crystallizing mother liquid disposal shaping of high silica alumina ratio MFI zeolite molecular sieves
The suitable condition of sieve is：100-200 DEG C for the treatment of temperature, preferably 150-170 DEG C；When processing time 2-100 is small, preferably 24-72 is small
When；Liquid-solid ratio 1-10, preferably 4-6；Mother liquor extension rate is not more than 20 times, preferably 5-10.
It is emphasized that the ammonium hexafluorosilicate benefit silicon measure taken in second step cannot be in the laggard of the 3rd step
Row.This is because in pH close to neutrality, ammonium hexafluorosilicate has a small amount of during benefit silicon is carried out to hydroxyl nest
The unformed oxidation silicon species plugging hole road of ammonium hexafluorosilicate hydrolysis generation.Therefore the siliceous duct tamper generated is needed the 3rd
Walk dissolving removal together in mother liquid disposal.
4th step, using conventional ion-exchange by the high silica alumina ratio MFI zeolite molecular sieve extruded mouldings of mother liquid disposal
Object is transformed into Hydrogen alkylation catalyst.Any engineer for being familiar with this field can exchange according to the conventional ion having disclosed
Method carries out practical operation.Ammonium salts such as ammonium nitrate or nitric acid, hydrochloric acid, sulfuric acid, citric acid and inorganic, organic can be used in ion exchange liquid
Acid configuration, does not repeat.
Beneficial effects of the present invention：The preparation process of alkylation catalyst by reduce catalyst activated centre density and with
Dredging catalyst duct two, which is arranged, develops simultaneously.Prepared catalyst can significantly reduce the hair of ethylbenzene and xylene isomerization side reaction
Life rate, so that the xylene product quality and benzene of benzene and methanol alkylation reaction production and ethanol alkylation reaction production
Ethylbenzene product Quality advance.Moreover, above-mentioned behave, along with ammonium hexafluorosilicate to making choice property of hydroxyl nest mend silicon
Processing, also greatly facilitates and slows down the coking and deactivation rate of catalyst in the reaction, extend the cycle of operation of catalyst.In addition,
The mother liquor generated when the present invention is by hydrothermal synthesis high silica alumina ratio MFI zeolite molecular sieves is used to handle the bar shaped catalyst after shaping,
The useful component in mother liquor has not only been recycled in this measure, has dredged the duct of catalyst, and it is complete to also reduce alkylation catalyst
Produce the environmental pollution in chain.
Specific embodiment
Below in conjunction with technical solution, the specific embodiment further illustrated the present invention.
Comparative example 1
Low silica-alumina ratio MFI zeolite molecular sieves is used to prepare benzene and methanol alkylation catalyst for parent.MFI zeolite molecular sieves
Silica alumina ratio be 60,125,160,215.Grain size is between 20-300 nanometers.The hydrothermal synthesis of above-mentioned molecular sieve is according to patent
The method that ZL201110364516.0 (a kind of synthetic method of ZSM-5 zeolite) is disclosed carries out.The extruded moulding of above-mentioned molecular sieve
Boehmite is used as binding agent, butt weight percent of the molecular sieve in the beaded catalyst of extruded moulding is
80%.Hydrogen type catalyst is made in the catalyst sample of above-mentioned extruded moulding according to usual way with 0.6N ammonium nitrate solutions.It will
Above-mentioned catalyst is used for benzene and methanol vapor phase alkylated reaction, is 400 DEG C, reaction pressure 1.0MPa in reaction temperature, benzene/first
Alcohol molar ratio is 2, and combined feed air speed is 2h-1Under conditions of, methanol conversion is all higher than 99%.With product group of the reaction 48 when small
Into being compared, in the C8 aronmatic product of the catalyst of silica alumina ratio 60,125,160,215, ethylbenzene impurity accounts for dimethylbenzene master
The percentage of product is followed successively by 50.6%, 40.6%, 37.3%, 31.8%.
Comparative example 2
Comparative example 1 is repeated, but obtained catalyst is being reacted for benzene and ethyl alcohol vapor phase alkylation
Temperature is 400 DEG C, reaction pressure 1.0MPa, and benzene/ethyl alcohol molar ratio is 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethyl alcohol
Conversion ratio is all higher than 99%.It is compared with product composition of the reaction 24 when small, 60,125,160,215 catalyst of silica alumina ratio
C8 aronmatic product in, accounting of the xylene impurities in ethylbenzene principal product is followed successively by 1000,900,830,750ppm.
Comparative example 3
High silica alumina ratio MFI zeolite molecular sieves is used to prepare benzene and methanol alkylation catalyst for parent.MFI zeolite molecular sieves
Silica alumina ratio for 800, grain size is between 200-300 nanometers.The hydrothermal synthesis of above-mentioned molecular sieve is according to patent
The method that ZL201110364516.0 (a kind of synthetic method of ZSM-5 zeolite) is disclosed carries out.The extruded moulding of above-mentioned molecular sieve
Boehmite is used as binding agent, butt weight percent of the molecular sieve in the beaded catalyst of extruded moulding is 80%.
Hydrogen type catalyst is made in the catalyst sample of above-mentioned extruded moulding according to usual way with 0.6N ammonium nitrate solutions.It is urged above-mentioned
Agent is used for benzene and methanol vapor phase alkylated reaction, is 400 DEG C, reaction pressure 1.0MPa in reaction temperature, benzene/Methanol Molar
Than for 2, combined feed air speed is 2h-1Under conditions of, methanol conversion is all higher than 99%.Negate answer 48 it is small when product analyzed
It calculates, the results showed that in C8 aronmatic product, the percentage that ethylbenzene impurity accounts for dimethylbenzene principal product is 16.2%.
Comparative example 4
Comparative example 3 is repeated, but is in reaction temperature for benzene and ethyl alcohol vapor phase alkylation by gained catalyst
400 DEG C, reaction pressure 1.0MPa, benzene/ethyl alcohol molar ratio is 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethanol conversion
It is all higher than 99%.Negate answer 24 it is small when product carry out analysis calculating, the results showed that in C8 aronmatic product, xylene impurities exist
Accounting in ethylbenzene principal product is 500ppm.
Embodiment 1
High silica alumina ratio MFI zeolite molecular sieves is used to prepare benzene and ethanol alkylation catalyst for parent.MFI zeolite molecular sieves
Silica alumina ratio for 800, grain size is between 200-300 nanometers.The hydrothermal synthesis of above-mentioned molecular sieve is according to patent
The method that ZL201110364516.0 (a kind of synthetic method of ZSM-5 zeolite) is disclosed carries out.The extrusion of above-mentioned zeolite molecular sieve
Shaping uses the estersil hydrolysate of acidifying as binding agent.Silicone grease hydrolysising condition is：Silicone grease/water ratio is 1.0, hydrolysis pH value ＜ 1.0,
Hydrolysis temperature is room temperature, hydrolysis time 0.5h.Hydrolysate solid content in negative pressure is except the jello after alcohol is 30wt.%.
Butt weight percent of the molecular sieve in the beaded catalyst of extruded moulding is 80%.With above-mentioned acidifying silicone grease hydrolysate and height
Silica alumina ratio MFI zeolite molecular sieves powder adds 3wt.% sesbania powders (with bar shaped catalyst butt weight when preparing extrusion material
Meter), addition 3wt.% atoleines (with bar shaped catalyst dry basis).Then, with the neutral aqueous solution of ammonium hexafluorosilicate
Silicon processing is mended to making choice property of extruded moulding catalyst.Actual conditions is：90 DEG C for the treatment of temperature, liquid-solid ratio 10, hexafluoro silicon
Sour aqueous ammonium concentration 0.03M, solution ph (adjust pH value) for 6 with tetrapropylammonium hydroxide, processing time 20h.To complete
The solid sample that silicon processing is mended into selectivity directly carries out (540 DEG C) processing of conventional drying (110 DEG C) and roasting.Then, use
Hydrothermal crystallizing silica alumina ratio is 800, and the separation that grain size obtains when being 200-300 nanometers of high silica alumina ratio MFI zeolite molecular sieves is female
Liquid handles extruded moulding object.Treatment conditions are：170 DEG C for the treatment of temperature, when processing time 24 is small, liquid-solid ratio 5, mother liquor extension rate
5.Finally, Hydrogen is made in the above-mentioned extruded moulding catalyst crossed through mother liquid disposal according to usual way with 0.6N ammonium nitrate solutions
Catalyst.By above-mentioned catalyst in benzene and ethyl alcohol vapor phase alkylation.It it is 400 DEG C in reaction temperature, reaction pressure is
1.0MPa, benzene/ethyl alcohol molar ratio are 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethanol conversion is more than 99%.It negates and answers 24
The product of hour carries out analysis calculating, the results showed that in C8 aronmatic product, accounting of the xylene impurities in ethylbenzene principal product
For 360ppm.The one way cycle of operation of the catalyst was more than 5 months.
Embodiment 2
Embodiment 1 is repeated, but is in reaction temperature for benzene and methanol vapor phase alkylated reaction by above-mentioned catalyst
400 DEG C, reaction pressure 1.0MPa, benzene/methanol molar ratio is 2, and combined feed air speed is 2h-1Under conditions of, methanol conversion is equal
More than 99%.Negate answer 48 it is small when product carry out analysis calculating, the results showed that in C8 aronmatic product, ethylbenzene impurity accounts for diformazan
The percentage of benzene principal product is 8.0%.The one way cycle of operation of the catalyst was more than 3 months.
Embodiment 3
Embodiment 1 is repeated, but the silica alumina ratio of used high silica alumina ratio MFI zeolite molecular sieves is 600, grain size exists
Between 200-300 nanometers.The hydrothermal synthesis of above-mentioned molecular sieve according to patent ZL201110364516.0 (a kind of ZSM-5 zeolite
Synthetic method) disclose method carry out.By above-mentioned catalyst in benzene and ethyl alcohol vapor phase alkylation.It is in reaction temperature
400 DEG C, reaction pressure 1.0MPa, benzene/ethyl alcohol molar ratio is 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethanol conversion
More than 99%.Negate answer 24 it is small when product carry out analysis calculating, the results showed that in C8 aronmatic product, xylene impurities are in second
Accounting in benzene principal product is 415ppm, and the one way cycle of operation of catalyst was more than 6 months.
Embodiment 4
Embodiment 1 is repeated, but the silica alumina ratio of used high silica alumina ratio MFI zeolite molecular sieves is 450, grain size exists
Between 200-300 nanometers.The hydrothermal synthesis of above-mentioned molecular sieve according to patent ZL201110364516.0 (a kind of ZSM-5 zeolite
Synthetic method) disclose method carry out.By above-mentioned catalyst in benzene and ethyl alcohol vapor phase alkylation.It is in reaction temperature
400 DEG C, reaction pressure 1.0MPa, benzene/ethyl alcohol molar ratio is 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethanol conversion
More than 99%.Negate answer 24 it is small when product carry out analysis calculating, the results showed that in C8 aronmatic product, xylene impurities are in second
Accounting in benzene principal product is 510ppm, and the one way cycle of operation of catalyst was more than 8 months.
Embodiment 5
Embodiment 1 is repeated, but directly Hydrogen, which is made, according to usual way with 0.6N ammonium nitrate solutions in extruded moulding object urges
Agent, and without hexafluorosilicic acid silicon processing and mother liquor dredging duct processing are mended by selectivity.By above-mentioned catalyst for benzene and
In ethyl alcohol vapor phase alkylation.It it is 400 DEG C, reaction pressure 1.0MPa in reaction temperature, benzene/ethyl alcohol molar ratio is 4, ethyl alcohol
Feed space velocities 0.7h-1Under conditions of, ethanol conversion is more than 99%.Negate answer 24 it is small when product carry out analysis calculating, as a result
Show in C8 aronmatic product, accounting of the xylene impurities in ethylbenzene principal product is 550ppm.The one way operation of the catalyst
Cycle is 3 months.
Embodiment 6
Embodiment 1 is repeated, but extruded moulding object is mended silicon by selectivity without hexafluorosilicic acid and handled.By above-mentioned catalyst
For in benzene and ethyl alcohol vapor phase alkylation.It is 400 DEG C, reaction pressure 1.0MPa in reaction temperature, benzene/ethyl alcohol molar ratio
For 4, ethyl alcohol Feed space velocities 0.7h-1Under conditions of, ethanol conversion is more than 99%.Negate answer 24 it is small when product carry out analysis meter
It calculates, the results showed that in C8 aronmatic product, accounting of the xylene impurities in ethylbenzene principal product is 420ppm.The list of the catalyst
The journey cycle of operation is 4 months.
Claims (10)
1. a kind of preparation method of highly selective anti-carbon benzene alkylation catalyst, which is characterized in that step is as follows：
The first step：Select parent of the high silica alumina ratio MFI zeolite molecular sieves as catalyst
The high silica alumina ratio MFI zeolite molecular sieves refer to the MFI molecular sieves that silica alumina ratio reaches more than 400, use hydro-thermal method
Synthesis；
Second step：It is mixed with acidifying silicone grease hydrolysate with high silica alumina ratio MFI zeolite molecular sieves, extruded moulding, then with hexafluoro silicon
The aqueous solution processing bar shaped molding of sour ammonium
The acidifying silicone grease hydrolysate refers to that the hydrolysate of ethyl orthosilicate in acid condition obtains after negative pressure removes alcohol
Jello；The hydrolysising condition selection of ethyl orthosilicate：The molar ratio of ethyl orthosilicate and water is 0.5-10, hydrolysis pH value ＜
7.0, hydrolysis temperature is room temperature, hydrolysis time 0.5-100h；Solid content control is in 20- in the acidifying silicone grease hydrolysate
In the range of 30wt.%；
When carrying out extruded moulding using above-mentioned acidifying silicone grease hydrolysate and high silica alumina ratio MFI zeolite molecular sieves, control in molding
High silica alumina ratio MFI zeolite molecular sieve contents in more than 60wt%；Bar shaped molding is dried and roasts according to Normal practice
Processing；
3rd step：The separation mother liquid disposal high silica alumina ratio MFI zeolites obtained during with hydrothermal crystallizing high silica alumina ratio MFI zeolite molecular sieves
The bar shaped molding of molecular sieve
With the high silica alumina ratio MFI zeolite molecular sieves after the hydrothermal crystallizing mother liquid disposal shaping of high silica alumina ratio MFI zeolite molecular sieves
Condition：Treatment temperature is 100-200 DEG C；When processing time is 2-100 small；Liquid-solid ratio is 1-10；Mother liquor extension rate is not more than
20 times；
4th step is changed the bar shaped molding of the high silica alumina ratio MFI zeolite molecular sieves after mother liquid disposal using ion-exchange
Into Hydrogen alkylation catalyst
The ion exchange liquid used in ion-exchange configures for ammonium salt, inorganic acid, organic acid.
2. preparation method according to claim 1, which is characterized in that boiled with acidifying silicone grease hydrolysate and high silica alumina ratio MFI
When stone molecular sieve prepares extrusion material, while adding liquid paraffin and sesbania powder auxiliary agent；Wherein, the addition of sesbania powder is bar shaped
The 3-5wt.% of molding butt weight, the addition of atoleine are the 1-3wt.% of bar shaped molding butt weight；Wherein,
The density of atoleine is 0.835-855, and recovered (distilled) temperature is 300 DEG C.
3. preparation method according to claim 1 or 2, which is characterized in that after second step, in ammonium hexafluorosilicate
Property aqueous solution silicon processing is mended to the making choice property of high silica alumina ratio MFI zeolite molecular sieve catalysts of extruded moulding, condition is：Processing
80-200 DEG C of temperature；Liquid-solid ratio is 1-20；Neutral aqueous solution the concentration 0.01-0.10M, pH value 6-7 of ammonium hexafluorosilicate；Processing
Time is 0.5-100h.
4. preparation method according to claim 1 or 2, which is characterized in that with the hydro-thermal of high silica alumina ratio MFI zeolite molecular sieves
The condition of high silica alumina ratio MFI zeolite molecular sieves after crystallization mother liquor processing shaping：Treatment temperature is 150-170 DEG C；Processing time
For 24-72 it is small when；Liquid-solid ratio is 4-6；Mother liquor extension rate is 5-10.
5. preparation method according to claim 3, which is characterized in that brilliant with the hydro-thermal of high silica alumina ratio MFI zeolite molecular sieves
Change the condition of the high silica alumina ratio MFI zeolite molecular sieves after mother liquid disposal shaping：Treatment temperature is 150-170 DEG C；Processing time is
When 24-72 is small；Liquid-solid ratio is 4-6；Mother liquor extension rate is 5-10.
6. according to the preparation method described in claim 1,2 or 5, which is characterized in that after second step, with ammonium hexafluorosilicate
Neutral aqueous solution mends silicon processing to the making choice property of high silica alumina ratio MFI zeolite molecular sieve catalysts of extruded moulding, and condition is：Place
It is 90-170 DEG C to manage temperature；Liquid-solid ratio is 5-10；Ammonium hexafluorosilicate concentration of aqueous solution 0.03-0.05M；Processing time is 10-
30h。
7. preparation method according to claim 3, which is characterized in that after second step, with the neutrality of ammonium hexafluorosilicate
Aqueous solution mends silicon processing to the making choice property of high silica alumina ratio MFI zeolite molecular sieve catalysts of extruded moulding, and condition is：Processing temperature
It spends for 90-170 DEG C；Liquid-solid ratio is 5-10；Ammonium hexafluorosilicate concentration of aqueous solution 0.03-0.05M；Processing time is 10-30h.
8. preparation method according to claim 4, which is characterized in that after second step, with the neutrality of ammonium hexafluorosilicate
Aqueous solution mends silicon processing to the making choice property of high silica alumina ratio MFI zeolite molecular sieve catalysts of extruded moulding, and condition is：Processing temperature
It spends for 90-170 DEG C；Liquid-solid ratio is 5-10；Ammonium hexafluorosilicate concentration of aqueous solution 0.03-0.05M；Processing time is 10-30h.
9. according to the preparation method described in claim 1,2,5,7 or 8, which is characterized in that the high silica alumina ratio MFI zeolites point
Son sieve refers to the MFI zeolite molecular sieves that silica alumina ratio is 500-1000；Other silicon of the hydrolysate acidifying of the acidifying silicone grease
Ester hydrolysis object replaces.
10. preparation method according to claim 6, which is characterized in that the high silica alumina ratio MFI zeolite molecular sieves refer to
Silica alumina ratio is the MFI zeolite molecular sieves of 500-1000；Other silicon ester hydrolysis of the hydrolysate acidifying of the acidifying silicone grease
Object replaces.
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| CN113600229A (en) * | 2021-09-13 | 2021-11-05 | 厦门大学 | Composite double-layer catalyst and method for preparing ethylbenzene and/or propylbenzene by carbon dioxide/carbon monoxide hydrogenation coupling benzene alkylation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244391A (en) * | 2008-03-18 | 2008-08-20 | 南京工业大学 | Process for producing fine grain ZSM-5 zeolite catalyst for methylbenzene selective dismutation |
| CN102463136A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Core-shell structure MFI molecular sieve and its preparation method |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
-
2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244391A (en) * | 2008-03-18 | 2008-08-20 | 南京工业大学 | Process for producing fine grain ZSM-5 zeolite catalyst for methylbenzene selective dismutation |
| CN102463136A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Core-shell structure MFI molecular sieve and its preparation method |
| CN102502696A (en) * | 2011-11-16 | 2012-06-20 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
Non-Patent Citations (1)
| Title |
|---|
| 徐海升等: "甲苯-甲醇在MF I 型沸石催化剂上的烷基化反应", 《石油学报(石油加工)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113600229A (en) * | 2021-09-13 | 2021-11-05 | 厦门大学 | Composite double-layer catalyst and method for preparing ethylbenzene and/or propylbenzene by carbon dioxide/carbon monoxide hydrogenation coupling benzene alkylation |
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