CN104923293B - Orthoresol isomerization catalyst, its preparation method and the method that M-and P-cresols is catalyzed and synthesized using it - Google Patents
Orthoresol isomerization catalyst, its preparation method and the method that M-and P-cresols is catalyzed and synthesized using it Download PDFInfo
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Abstract
The present invention provides a kind of orthoresol isomerization catalyst, and in terms of weight/mass percentage composition, the catalyst is made up of 65% ~ 95% composite molecular screens of H type MCM 41/ZSM 5 and 5% ~ 35% binding agent.The method that the present invention is also provided a kind of preparation method of orthoresol isomerization catalyst and M-and P-cresols is catalyzed and synthesized using it.Above-mentioned orthoresol isomerization catalyst, first with silicon source, silicon source etc. for raw material, in the basic conditions Na type composite molecular screens are synthesized using cetyl trimethylammonium bromide and 4-propyl bromide as the step crystallization method of template two, H type composite molecular screens are synthesized through ion exchange again, are finally formed again with binding agent mixed-forming.The catalyst has greater activity and stability, and is remarkably improved the selectivity of M-and P-cresols, is suitable for using in fixed bed reactors.
Description
Technical field
The present invention relates to orthoresol isomerization catalyst, more particularly to a kind of orthoresol isomerization catalyst, its preparation
Method and the method that M-and P-cresols is catalyzed and synthesized using it.
Background technology
M-and P-cresols is a certain proportion of metacresol and paracresol mixture, is a kind of important chemical intermediate, extensively
For fields such as agricultural chemicals, plastics, medicine, wire enamels, while be also the important materials for producing metacresol and paracresol, for example,
Using isobutene reaction method, urea complexation crystallisation, high-purity metacresol can be obtained, and can be obtained respectively using adsorbing separation rule
Obtain high-purity metacresol and paracresol.
In eighties of last century, the approach that people obtain M-and P-cresols is mainly naturally isolated method, i.e., separated from coal tar
Arrive.Separation can obtain phenol, orthoresol, M-and P-cresols and xylenol etc. from coal tar.But it is due to resource-constrained, technique
Complexity, after chemical synthesis succeeds, naturally isolated device is constantly eliminated.Neighbour can be synthesized by chemical synthesis
Cresols, paracresol and metacresol, xylenol, can also synthesize M-and P-cresols, and main method has parachlorotoluene Hydrolyze method and adjacent first
Phenol isomerization process, alkylation of phenol method etc..
For M-and P-cresols product, because the content of metacresol contained by it is different, its market price is otherwise varied, and meta contains
Amount is higher, is more favored by market.Therefore, compared with the M-and P-cresols directly separated from coal tar, with orthoresol isomery
Changing produced M-and P-cresols product has meta high（Metacresol content is more than 75%）Advantage.Relative to ortho-chlorotolu'ene hydrolysis
Method, orthoresol isomerization production M-and P-cresols is the new technology of environmental protection.
Molecular screen material（Especially micro porous molecular sieve）It is isomerization reaction, alkylated reaction, disproportionated reaction and alkyl
Change the class catalysis material commonly used in transfer reaction, be widely used in the every field of petrochemical industry.
United States Patent (USP) US4503269, which discloses H types ZSM-5 molecular sieve, to be used between orthoresol isomerization reaction synthesis to first
Phenol, the technique uses autoclave and fixed bed reactors.A large amount of phenol and xylenol are had in autoclave course of reaction
Produced Deng accessory substance, M-and P-cresols is selectively relatively low.In fixed bed reactors, side reaction is few, and by-product phenol yield is 4%
Hereinafter, M-and P-cresols total recovery is up to 50.5%, but catalyst life is short, and industrialization cost is higher.
United States Patent (USP) US4691063 is used for orthoresol after disclosing the shaping of H type ZSM-5 molecular sieves Ludox and P Modification
Isomerization reaction synthesizes M-and P-cresols, and after reacting 4 hours, phenol yield is 3.8%, and M-and P-cresols total recovery is up to 52.0%.
But after reaction is carried out 20 hours, catalyst activity is just substantially reduced, if for fixed bed reactors, needing frequent regeneration,
Industrialization is relatively difficult.
Patent CN103341363A is disclosed between a kind of orthoresol isomerization production, the fluidized catalyzing method of paracresol, wherein
The catalyst being related to just includes molecular sieve series material, but such catalyst life is shorter, is not suitable for fixed bed reactors, only
Fluidized-bed process can be used, complexity is set, operation difficulty is big, and production cost is higher.
Patent CN103341363A is disclosed between a kind of orthoresol isomerization production, the movable bed catalyst of paracresol and its system
Preparation Method.Its catalyst uses the modified gained of H type ZSM-5 molecular sieves, also due to the reason for catalyst life is too short,
Only it is applicable and uses moving bed reaction device, the complex process equipment, automaticity requires higher, and operation difficulty is big, it is difficult to work
Industry.
In summary, traditional orthoresol isomery is combined to M-and P-cresols catalyst activity is low, the choosing of short life, M-and P-cresols
Selecting property is relatively low, and is not suitable for fixed bed device.
The content of the invention
Based on this, it is necessary to for traditional orthoresol isomerization catalyst activity is low, short life, M-and P-cresols selectivity
It is relatively low, and there is provided a kind of active height, long lifespan, M-and P-cresols selectivity are higher the problem of be not suitable for fixed bed device, and fit
Orthoresol isomerization catalyst for fixed bed device.
The present invention also provides a kind of preparation method of orthoresol isomerization catalyst.
In addition, the present invention also provides a kind of method that utilization orthoresol isomerization catalyst catalyzes and synthesizes M-and P-cresols.
A kind of orthoresol isomerization catalyst, in terms of weight/mass percentage composition, the catalyst by 65% ~ 95% H types MCM-
41/ZSM-5 composite molecular screens and 5% ~ 35% binding agent composition.
In one of the embodiments, the binding agent is selected from least one of aluminum oxide and silica.
In one of the embodiments, in the H types MCM-41/ZSM-5 composite molecular screens mol ratio of silicon and aluminium for 30 ~
45:2。
A kind of preparation method of orthoresol isomerization catalyst, comprises the following steps：
H type MCM-41/ZSM-5 composite molecular screens and binding agent are mixed, mixture is obtained；And
By mixture kneading, shaping, dry roasting, catalyst is obtained, in terms of weight/mass percentage composition, the catalysis
Agent is made up of 65% ~ 95% H type MCM-41/ZSM-5 composite molecular screens and 5% ~ 35% binding agent.
In one of the embodiments, the H types MCM-41/ZSM-5 composite molecular screens are prepared by following methods：
Using cetyl trimethylammonium bromide as template, silicon source, silicon source, alkali source and deionized water stirring mixing are added,
Obtain mixed liquor；
The pH value of the mixed liquor is modulated 10 ~ 11.5, in 95 ~ 110 DEG C of crystallization 1 ~ 24 hour, sial precursor is obtained；
And
The sial precursor is mixed with 4-propyl bromide, 120 ~ 135 DEG C, pH=9 ~ 10, crystallization 48 ~ 96 hours,
Through filtering, washing, dry, roasting, Na type MCM-41/ZSM-5 composite molecular screens are obtained；And
The Na types MCM-41/ZSM-5 composite molecular screens are mixed with 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solutions,
The ratio of the Na types MCM-41/ZSM-5 composite molecular screens and the aqueous ammonium nitrate solution is 1:1000g/ml~10:1000g/
Ml, ion exchange is carried out 3 ~ 10 hours at 70 ~ 90 DEG C, through filtering, washing, dry, roasting, is obtained H types MCM-41/ZSM-5 and is answered
The mol ratio for closing silicon and aluminium in molecular sieve, the H types MCM-41/ZSM-5 composite molecular screens is 30 ~ 45:2.
In one of the embodiments, it is described by mixture kneading, shaping, dry roasting, obtain catalyst
In step, the temperature of the roasting is 450 DEG C ~ 600 DEG C；
It is described to be obtained through filtering, washing, dry, roasting in the step of Na type MCM-41/ZSM-5 compound molecules shine, it is described
The temperature of roasting is 450 DEG C ~ 600 DEG C；
It is described to be obtained through filtering, washing, dry, roasting in the step of H type MCM-41/ZSM-5 compound molecules shine, it is described
The temperature of roasting is 450 DEG C ~ 600 DEG C.
In one of the embodiments, the binding agent is selected from least one of aluminum oxide and silica.
A kind of method that utilization orthoresol isomerization catalyst catalyzes and synthesizes M-and P-cresols, comprises the following steps：
By orthoresol in the presence of carrier gas with catalyst in fixed bed reactors haptoreaction, obtain M-and P-cresols, with
Weight/mass percentage composition meter, the catalyst is by 65% ~ 95% H type MCM-41/ZSM-5 composite molecular screens and 5% ~ 35% binding agent
Composition.
In one of the embodiments, it is described to connect orthoresol in fixed bed reactors with catalyst in the presence of carrier gas
In the step of touching reaction, the condition of the reaction is specially：Temperature is 300 DEG C ~ 450 DEG C, and pressure is 0.2MPa ~ 3.5MPa, adjacent
The mass space velocity of cresols is 0.1 h-1~4.0h-1。
In one of the embodiments, it is described to connect orthoresol in fixed bed reactors with catalyst in the presence of carrier gas
In the step of touching reaction, the condition of the reaction is specially：Temperature is 330 DEG C ~ 390 DEG C, and pressure is 0.5MPa ~ 2.5MPa, adjacent
The mass space velocity of cresols is 0.5h-1~2.5h-1。
Above-mentioned orthoresol isomerization catalyst, with silicon source, silicon source etc. for raw material, in the basic conditions, with cetyl three
Methyl bromide ammonium and 4-propyl bromide are crystallized in two steps for template to be formed, and the catalyst has greater activity and stability,
And the selectivity of M-and P-cresols is remarkably improved, it is suitable for using in fixed bed reactors.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, specific reality below to the present invention
The mode of applying is described in detail.Many details are elaborated in the following description to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
A kind of orthoresol isomerization catalyst, by the H type MCM-41/ZSM-5 compound molecules of 65% ~ 95% weight/mass percentage composition
The binding agent of sieve and 5% ~ 35% weight/mass percentage composition is constituted.
Wherein, the mol ratio of silicon and aluminium is 30 ~ 45 in H types MCM-41/ZSM-5 composite molecular screens:2.
Binding agent is selected from least one of aluminum oxide and silica.
In the present embodiment, binding agent is selected from hydrated alumina（Such as boehmite or boehmite）And Ludox
At least one of.
Molecular sieve is the natural or artificial synthesized chemical substance with network structure.According to it is international purely and applied chemistry
Association（IUPAC）Definition, porous material can be divided into three classes by the difference in aperture：Aperture be less than 2.0nm for micropore, have
The material of regular micropore canals is referred to as containing Microporous Compounds, such as ZSM-5, Y, Bete, MCM-22；Aperture is 2.0nm ~ 50nm's
Mesoporous, the material with ordered mesoporous pore canals structure is referred to as mesoporous material, such as MCM-41, MCM-48, SBA-5；Aperture is more than
50nm material is referred to as large pore material.
Micro porous molecular sieve has highly acid and hydrothermal stability, but because aperture is small, major diameter molecule is difficult to enter its hole
Road, and react in duct the macromolecular of generation and can not quickly escape, often results in side reaction, make its application by
Limitation.The uniform single, hole wall in mesopore molecular sieve aperture is relatively thin, is easily collapsed under high temperature or hydrothermal condition.
The H type MCM-41/ZSM-5 composite molecular screens that above-mentioned orthoresol isomerization catalyst contains are compound for micropore-mesopore
Molecular sieve, can overcome the defect of single micropore, mesopore molecular sieve, make two kinds of material advantage complementations, then be combined with binding agent, make
The catalyst has greater activity and stability.
The preparation method of the orthoresol isomerization catalyst of one embodiment, comprises the following steps：
S110, with cetyl trimethylammonium bromide（CTAB）For template, silicon source, silicon source, alkali source and deionization are added
Water stirring mixing, obtains mixed liquor.
Wherein, silicon source is selected from least one of Ludox, tetraethyl orthosilicate and white carbon.Silicon source is aluminum sulfate, meta-aluminic acid
Sodium or aluminum nitrate.Alkali source is sodium hydroxide.
The addition of above-mentioned silicon source is converted into Al2O3Addition, the addition of silicon source is converted into SiO2Addition,
Then Al2O3With SiO2Mol ratio be 0.02 ~ 0.035:1, CTAB and SiO2Mol ratio be 0.08 ~ 0.30:1, NaOH and SiO2
Mol ratio be 0.15 ~ 0.2:1.
S120, the pH value of above-mentioned mixed liquor is adjusted to 10 ~ 11.5, in 95 DEG C ~ 110 DEG C crystallization 1 ~ 24 hour, obtains sial
Precursor.
Wherein, the method for the pH value of above-mentioned mixed liquor being adjusted into 10 ~ 11.5 is specially：Using 30% ~ 50% mass concentration
The pH value of mixed liquor is adjusted to 10 ~ 11.5 by sulfuric acid.
S130, by above-mentioned sial precursor and 4-propyl bromide（TPABr）Mixing, it is brilliant 120 ~ 135 DEG C, pH=9 ~ 10
Change 48 ~ 96 hours, Na type MCM-41/ZSM-5 composite molecular screens are obtained through filtering, washing, dry, roasting.
Wherein TPABr and SiO2Mol ratio be 0.12 ~ 0.4:1.
Changed by modulation crystallization time in 48 ~ 96 hours, Na type MCM-41/ZSM-5 composite molecular screens can be adjusted
The ratio of intermediary hole-micropore.
It is above-mentioned through filtering, washing, dry, roasting obtain Na type MCM-41/ZSM-5 composite molecular screens the step of in, roasting
Temperature be 450 DEG C ~ 600 DEG C.
S140, by above-mentioned Na types MCM-41/ZSM-5 composite molecular screens and 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solutions
Mixing, ion exchange is carried out 3 ~ 10 hours at 70 ~ 90 DEG C, through filtering, washing, dry, roasting, obtains H types MCM-41/ZSM-5
Composite molecular screen.
Wherein, the ratio of Na types MCM-41/ZSM-5 composite molecular screens and aqueous ammonium nitrate solution is 1:100g/ml~10:
1000g/ml。
The mol ratio of silicon and aluminium is 30 ~ 45 in H type MCM-41/ZSM-5 composite molecular screens:2.
It is above-mentioned through filtering, washing, dry, roasting, in the step of obtaining H type MCM-41/ZSM-5 composite molecular screens, roasting
Temperature be 450 DEG C ~ 600 DEG C.
S150, above-mentioned H types MCM-41/ZSM-5 composite molecular screens and binding agent mixed, obtain mixture.
Wherein, binding agent is selected from least one of aluminum oxide and silica.
In the present embodiment, binding agent is selected from hydrated alumina（Such as boehmite or boehmite）And Ludox
At least one of.
S160, said mixture mediated, is molded, dry roasting, obtain catalyst.
Wherein, catalyst is by the H type MCM-41/ZSM-5 composite molecular screens of 65% ~ 95% weight/mass percentage composition and 5% ~ 35% matter
Measure the binding agent composition of percentage composition.
In the present embodiment, said mixture is mediated, is molded, dry roasting, in the step of obtaining catalyst, roasting
The temperature of burning is 450 DEG C ~ 600 DEG C.It is preferred that, the temperature of roasting is 550 DEG C.
It should be noted that above-mentioned H types MCM-41/ZSM-5 composite molecular screens are not limited to step S110 ~ S140's of the above
Preparation method, in other embodiments, H type MCM-41/ZSM-5 composite molecular screens can also using other method prepare or
Directly purchase is obtained.
The preparation method of above-mentioned orthoresol isomerization catalyst is simple, with silicon source, silicon source etc. for raw material, in alkalescence condition
Under, the catalyst for forming, preparing is crystallized as template using cetyl trimethylammonium bromide and 4-propyl bromide in two steps
With greater activity and stability, it is suitable for using in fixed bed reactors.
A kind of method that utilization orthoresol isomerization catalyst catalyzes and synthesizes M-and P-cresols, comprises the following steps：By adjacent first
Phenol in the presence of carrier gas with catalyst in fixed bed reactors haptoreaction, obtain M-and P-cresols.
Wherein, catalyst is by the H type MCM-41/ZSM-5 composite molecular screens of 65% ~ 95% weight/mass percentage composition and 5% ~ 35% matter
Measure the binding agent composition of percentage composition.
The mol ratio of silicon and aluminium is 30 ~ 45 in H type MCM-41/ZSM-5 composite molecular screens:2.
Binding agent is selected from least one of aluminum oxide and silica.
Specifically, catalytic condition is in fixed bed reactors with catalyst in the presence of carrier gas by orthoresol：
Temperature is 300 DEG C ~ 450 DEG C, and pressure is 0.2MPa ~ 3.5MPa, and the mass space velocity of orthoresol is 0.1h-1~4.0h-1。
It is preferred that, by orthoresol, catalytic condition is in fixed bed reactors with catalyst in the presence of carrier gas：
Temperature is 330 DEG C ~ 390 DEG C, and pressure is 0.5MPa ~ 2.5MPa, and the mass space velocity of orthoresol is 0.5h-1~2.5h-1。
The method that above-mentioned utilization orthoresol isomerization catalytic synthesizes M-and P-cresols, is remarkably improved the selection of M-and P-cresols
Property.
It is specific embodiment below.
Embodiment 1
（1）The preparation of H type MCM-41/ZSM-5 composite molecular screens
Using 17.5g cetyl trimethylammonium bromides as template, 60g Ludox, 3.65g aluminum nitrates, 2.28g hydrogen are added
Sodium oxide molybdena and the stirring mixing of 450g deionized waters, obtain mixed liquor.
Above-mentioned mixed liquor pH value is adjusted to 11 with the sulfuric acid of mass concentration 50%, in 100 DEG C of crystallization 12 hours, obtains sial first
Drive body.
Above-mentioned sial precursor is mixed with 4-propyl bromide, 125 DEG C, pH=9.5, crystallization 48 hours, through filtering,
Washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screens.
Above-mentioned Na types MCM-41/ZSM-5 composite molecular screens are weighed into 10g and are dissolved in 1000ml aqueous ammonium nitrate solutions（0.5mol/
L）Mixing, ion exchange is carried out 4 hours at 80 DEG C, through filtering, washing, dry, roasting, is obtained H types MCM-41/ZSM-5 and is combined
Molecular sieve.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types MCM-41/ZSM-5 composite molecular screens and aluminum oxide are mixed, mediates, are molded, drying after 550 DEG C of roastings
Burning obtains catalyst, and the catalyst is designated as MZM-1.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-1 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 54.5%, and the selectivity of M-and P-cresols is 98.0%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-1 in the presence of carrier gas
When, the conversion ratio of orthoresol is 52.8%, and the selectivity of M-and P-cresols is 98.5%.
Embodiment 2
（1）The preparation of H type MCM-41/ZSM-5 composite molecular screens
Using 17.5g cetyl trimethylammonium bromides as template, 60g Ludox, 3.65g aluminum nitrates, 2.28g hydrogen are added
Sodium oxide molybdena and the stirring mixing of 450g deionized waters, obtain mixed liquor.
Above-mentioned mixed liquor pH value is adjusted to 11 with the sulfuric acid of mass concentration 50%, in 100 DEG C of crystallization 12 hours, obtains sial first
Drive body.
Above-mentioned sial precursor is mixed with 4-propyl bromide, 125 DEG C, pH=9.5, crystallization 72 hours, through filtering,
Washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screens.
Above-mentioned Na types MCM-41/ZSM-5 composite molecular screens are weighed into 10g and are dissolved in 1000ml aqueous ammonium nitrate solutions（0.5mol/
L）Mixing, ion exchange is carried out 4 hours at 80 DEG C, through filtering, washing, dry, roasting, is obtained H types MCM-41/ZSM-5 and is combined
Molecular sieve.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types MCM-41/ZSM-5 composite molecular screens and aluminum oxide are mixed, mediates, are molded, drying after 550 DEG C of roastings
Burning obtains catalyst, and the catalyst is designated as MZM-2.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-2 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 57.9%, and the selectivity of M-and P-cresols is 98.8%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-2 in the presence of carrier gas
When, the conversion ratio of orthoresol is 56.8%, and the selectivity of M-and P-cresols is 99.2%.
Embodiment 3
（1）The preparation of H type MCM-41/ZSM-5 composite molecular screens
Using 17.5g cetyl trimethylammonium bromides as template, 60g Ludox, 3.65g aluminum nitrates, 2.28g hydrogen are added
Sodium oxide molybdena and 450g deionized waters add stirring mixing in certain sequence, obtain mixed liquor.
Above-mentioned mixed liquor pH value is adjusted to 11 with the sulfuric acid of mass concentration 50%, in 100 DEG C of crystallization 12 hours, obtains sial first
Drive body.
Above-mentioned sial precursor is mixed with 4-propyl bromide, 125 DEG C, pH=9.5, crystallization 96 hours, through filtering,
Washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screens.
Above-mentioned Na types MCM-41/ZSM-5 composite molecular screens are weighed into 10g and are dissolved in 1000ml aqueous ammonium nitrate solutions（0.5mol/
L）Mixing, ion exchange is carried out 4 hours at 80 DEG C, through filtering, washing, dry, roasting, is obtained H types MCM-41/ZSM-5 and is combined
Molecular sieve.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types MCM-41/ZSM-5 composite molecular screens and aluminum oxide are mixed, mediates, are molded, drying after 550 DEG C of roastings
Burning obtains catalyst, and the catalyst is designated as MZM-3.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-3 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 53.2%, and the selectivity of M-and P-cresols is 97.2%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-3 in the presence of carrier gas
When, the conversion ratio of orthoresol is 51.4%, and the selectivity of M-and P-cresols is 97.9%.
Comparative example 1
（1）The preparation of H type MCM-41 molecular sieves
The former powder of mesostructured material is weighed into 10g and is dissolved in 1000ml aqueous ammonium nitrate solutions（0.5mol/L）Mixing,
The ion exchange of 80 DEG C of progress 4 hours, H types MCM-41 is obtained after filtering, washing, drying.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types MCM-41 and aluminum oxide are mixed, mediates, are molded, drying obtains catalyst after 550 DEG C of roastings, should
Catalyst is designated as MZM-4.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-4 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 40.8%, and the selectivity of M-and P-cresols is 96.0%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-4 in the presence of carrier gas
When, the conversion ratio of orthoresol is 35.5%, and the selectivity of M-and P-cresols is 97.3%.
Comparative example 2
（1）The preparation of H type ZSM-5 molecular sieves
The former powder of ZSM-5 molecular sieve is weighed into 10g and is dissolved in 1000ml aqueous ammonium nitrate solutions（0.5mol/L）Mixing, enters at 80 DEG C
The row ion exchange of 4 hours, H type ZSM-5 molecular sieves are obtained after filtering, washing, drying.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types ZSM-5 molecular sieve and aluminum oxide are mixed, mediates, are molded, drying is catalyzed after 550 DEG C of roastings
Agent, the catalyst is designated as MZM-5.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-5 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 60.5%, and the selectivity of M-and P-cresols is 91.1%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-5 in the presence of carrier gas
When, the conversion ratio of orthoresol is 40.6%, and the selectivity of M-and P-cresols is 95.8%.
Comparative example 3
（1）The preparation of H type MCM-41/ZSM-5 composite molecular screens
H types ZSM-5 molecular sieve described in H types MCM-41 described in comparative example 1 and comparative example 2 is pressed 1：1 ratio machinery is mixed
Close, obtain H type MCM-41/ZSM-5 composite molecular screens.
（2）The preparation of orthoresol isomerization catalyst
Above-mentioned H types MCM-41/ZSM-5 composite molecular screens and aluminum oxide are mixed, mediates, are molded, drying after 550 DEG C of roastings
Burning obtains catalyst, and the catalyst is designated as MZM-6.
（3）M-and P-cresols is catalyzed and synthesized
By orthoresol in the presence of carrier gas with above-mentioned catalyst MZM-6 in fixed bed reactors haptoreaction 5 hours, it is adjacent
The conversion ratio of cresols is 53.2%, and the selectivity of M-and P-cresols is 93.5%.
By orthoresol, haptoreaction 1000 is small in fixed bed reactors with above-mentioned catalyst MZM-6 in the presence of carrier gas
When, the conversion ratio of orthoresol is 46.7%, and the selectivity of M-and P-cresols is 94.2%.
H type MCM-41/ZSM-5 composite molecular screens in embodiment 1 ~ 3 are by weakly acidic MCM-41 molecular sieves and highly acid
ZSM-5 molecular sieve be composited in microcosmic point, relative to the mechanical impurity of both macroscopic aspects in comparative example 3, its acid
Property central distribution it is uniform, acid intensity is suitable, is more beneficial for the progress of isomerization reaction, with higher activity and selectivity,
The carbon distribution speed of acid centre is also slow down simultaneously.
Further, since the micropore-mesopore structure of the H type MCM-41/ZSM-5 composite molecular screens uniqueness in embodiment 1 ~ 3, phase
For single H type ZSM-5 molecular sieves in comparative example 2, be more beneficial for the mass transfer of course of reaction so that reactant can and
Time shift goes out duct, reduces the generation of side reaction, meanwhile, can also reduce molecular sieve causes duct to block due to carbon distribution, covering
The activated centre of molecular sieve, so as to improve the selectivity and service life of catalyst.
In a word, H type MCM-41 molecular sieves are used alone as the catalyst of orthoresol isomerization reaction, its acid strength is not
Enough, reactivity is relatively low, and H type ZSM-5 molecular sieves are used alone and make catalyst, then because it is acid stronger, duct is smaller, urges
The easy carbon distribution of agent and rapid deactivation, catalyst life are shorter, and accessory substance is more.And H type MCM-41/ZSM-5 composite molecular screens
The catalyst set respective advantage of MCM-41 molecular sieves and ZSM-5 molecular sieve, existing higher catalysis orthoresol isomerization is anti-
The activity and selectivity answered, while also having longer service life, is suitable for fixed bed reaction technique.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (7)
1. a kind of orthoresol isomerization catalyst, it is characterised in that in terms of weight/mass percentage composition, the catalyst is by 65% ~ 95%
H type MCM-41/ZSM-5 composite molecular screens and 5% ~ 35% binding agent composition；
The binding agent is selected from least one of aluminum oxide and silica；The H types MCM-41/ZSM-5 composite molecular screens
The mol ratio of middle silicon and aluminium is 30 ~ 45:2.
2. a kind of preparation method of orthoresol isomerization catalyst, it is characterised in that comprise the following steps：
H type MCM-41/ZSM-5 composite molecular screens and binding agent are mixed, mixture is obtained；And
By the mixture mediate, shaping, dry roasting obtains catalyst, in terms of weight/mass percentage composition, the catalyst by
65% ~ 95% H type MCM-41/ZSM-5 composite molecular screens and 5% ~ 35% binding agent composition；
The binding agent is selected from least one of aluminum oxide and silica；The H types MCM-41/ZSM-5 composite molecular screens
The mol ratio of middle silicon and aluminium is 30 ~ 45:2.
3. the preparation method of orthoresol isomerization catalyst according to claim 2, it is characterised in that the H types MCM-
41/ZSM-5 composite molecular screens are prepared by following methods：
Using cetyl trimethylammonium bromide as template, silicon source, silicon source, alkali source and deionized water stirring mixing are added, is obtained
Mixed liquor；
The pH value of the mixed liquor is adjusted to 10 ~ 11.5, in 95 ~ 110 DEG C of crystallization 1 ~ 24 hour, sial precursor is obtained；
The sial precursor is mixed with 4-propyl bromide, 120 ~ 135 DEG C, pH=9 ~ 10, crystallization 48 ~ 96 hours is passed through
Filter, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screens；And
The Na types MCM-41/ZSM-5 composite molecular screens are mixed with 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solutions, it is described
The ratio of Na type MCM-41/ZSM-5 composite molecular screens and the aqueous ammonium nitrate solution is 1:100g/mL~10:1000g/mL,
70 ~ 90 DEG C carry out ion exchange 3 ~ 10 hours, through filtering, washing, dry, roasting, obtain H type MCM-41/ZSM-5 compound molecules
The mol ratio of silicon and aluminium is 30 ~ 45 in sieve, the H types MCM-41/ZSM-5 composite molecular screens:2.
4. the preparation method of orthoresol isomerization catalyst according to claim 3, it is characterised in that described described to mix
Compound is mediated, is molded, dry roasting, in the step of obtaining catalyst, and the temperature of the roasting is 450 DEG C ~ 600 DEG C；
It is described through filtering, washing, dry, roasting, in the step of obtaining Na type MCM-41/ZSM-5 composite molecular screens, the roasting
Temperature be 450 DEG C ~ 600 DEG C；
It is described through filtering, washing, dry, roasting, in the step of obtaining H type MCM-414/ZSM-5 composite molecular screens, the roasting
Temperature be 450 DEG C ~ 600 DEG C.
5. a kind of method that utilization orthoresol isomerization catalyst catalyzes and synthesizes M-and P-cresols, it is characterised in that including following step
Suddenly：
By orthoresol in the presence of carrier gas with catalyst in fixed bed reactors haptoreaction, M-and P-cresols is obtained, with quality
Percentage composition meter, H type MCM-41/ZSM-5 composite molecular screen and 5% ~ 35% binding agent group of the catalyst by 65% ~ 95%
Into；The binding agent is selected from least one of aluminum oxide and silica；In the H types MCM-41/ZSM-5 composite molecular screens
The mol ratio of silicon and aluminium is 30 ~ 45:2.
6. the method that utilization orthoresol isomerization catalyst according to claim 5 catalyzes and synthesizes M-and P-cresols, its feature
Be, it is described by orthoresol the step of in the presence of carrier gas with catalyst haptoreaction in fixed bed reactors in, it is described anti-
The condition answered is specially：Temperature is 300 DEG C ~ 450 DEG C, and pressure is 0.2MPa ~ 3.5MPa, and the mass space velocity of orthoresol is 0.1h-1~
4.0h-1。
7. the method that utilization orthoresol isomerization catalyst according to claim 5 catalyzes and synthesizes M-and P-cresols, its feature
Be, it is described by orthoresol the step of in the presence of carrier gas with catalyst haptoreaction in fixed bed reactors in, it is described anti-
The condition answered is specially：Temperature is 330 DEG C ~ 390 DEG C, and pressure is 0.5MPa ~ 2.5MPa, and the mass space velocity of orthoresol is 0.5h-1~
2.5h-1。
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| RU2702586C1 (en) * | 2019-05-21 | 2019-10-08 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Micro-mesoporous xylene isomerisation catalyst |
| CN113351243B (en) * | 2021-06-21 | 2022-12-30 | 山西大学 | Catalyst for producing m-cresol from o-cresol in isomeric mode and preparation method of catalyst |
| CN113731476B (en) * | 2021-06-23 | 2023-10-03 | 浙江环化科技有限公司 | Method for producing m-cresol |
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| CN115155650B (en) * | 2022-08-01 | 2024-03-19 | 浙江医药股份有限公司新昌制药厂 | Catalyst and preparation method and application thereof |
| CN115445653B (en) * | 2022-09-01 | 2023-04-18 | 宁夏派可威生物科技有限公司 | Preparation process of cresol isomerization catalyst |
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