CN104923293A - O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst - Google Patents
O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst Download PDFInfo
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Abstract
The invention provides an o-cresol isomerization catalyst. The o-cresol isomerization catalyst comprises, by mass, 65%-95% of H-type MCM-41/ZSM-5 composite molecular sieves and 5%-35% of binders. The invention further provides a preparing method of the o-cresol isomerization catalyst and a method for catalyzed synthesis of a mixture of m-cresol and p-cresol through the o-cresol isomerization catalyst. The preparing method of the o-cresol isomerization catalyst includes the steps that a silicon source, an aluminum source and the like serve as raw materials firstly, hexa decyl trimethyl ammonium bromide and tetra propyl ammonium ammonium bromide serve as templates under the alkaline condition so as to synthesize Na-type composite molecular sieves with a two-step crystallization method, then the H-type composite molecular sieves are synthesized through ion exchange, and finally the H-type composite molecular sieves and the binders are mixed and molded. The o-cresol isomerization catalyst has the higher activity and the higher stability, and the selectivity of the mixture of the m-cresol and the p-cresol can be obviously improved, and the o-cresol isomerization catalyst is suitable for a fixed bed reactor.
Description
Technical field
The present invention relates to orthoresol isomerization catalyst, particularly relate to a kind of orthoresol isomerization catalyst, its preparation method and utilize it to catalyze and synthesize the method for M-and P-cresols.
Background technology
M-and P-cresols is a certain proportion of metacresol and paracresol mixture, it is a kind of important chemical intermediate, be widely used in the fields such as agricultural chemicals, plastics, medicine, wire enamel, also be the important materials of producing metacresol and paracresol simultaneously, such as, adopt isobutene reaction method, urea complexation crystallisation, high-purity metacresol can be obtained, and adopt adsorbing separation rule can obtain high-purity metacresol and paracresol respectively.
In eighties of last century, people obtain the approach mainly natural partition method of M-and P-cresols, are namely separated from coal tar and obtain.Be separated from coal tar and can obtain phenol, orthoresol, M-and P-cresols and xylenol etc.But due to resource-constrained, complex process, after chemical synthesis succeeds, natural separator is constantly eliminated.By chemical synthesis can synthesizing o-cresol, paracresol and metacresol, xylenol, also can synthesize M-and P-cresols, main method has parachlorotoluene Hydrolyze method and orthoresol isomerization process, alkylation of phenol method etc.
With regard to M-and P-cresols product, because the content of metacresol contained by it is different, its market price is distinguished to some extent, and a position content is higher, more favors by market.Therefore, compared with the direct M-and P-cresols separated from coal tar, the advantage of position high (metacresol content is greater than 75%) between the M-and P-cresols product produced with orthoresol isomerization has.Relative to ortho-chlorotolu'ene Hydrolyze method, the new technology that M-and P-cresols is environmental protection is produced in orthoresol isomerization.
Molecular screen material (especially micro porous molecular sieve) is a class catalysis material conventional in isomerization reaction, alkylated reaction, disproportionated reaction and transalkylation reaction, is widely used in the every field of petrochemical industry.
US Patent No. 4503269 discloses H type ZSM-5 molecular sieve for orthoresol isomerization reaction synthesis M-and P-cresols, and this technique adopts autoclave and fixed bed reactors.In autoclave course of reaction, have the accessory substances such as a large amount of phenol and xylenol produce, M-and P-cresols is selective lower.In fixed bed reactors, side reaction is few, and by-product phenol yield is below 4%, and M-and P-cresols total recovery is up to 50.5%, but catalyst life is short, and industrialization cost is higher.
US Patent No. 4691063 discloses for orthoresol isomerization reaction synthesis M-and P-cresols after the shaping and P Modification of H type ZSM-5 molecular sieve Ludox, and react after 4 hours, phenol yield is 3.8%, and M-and P-cresols total recovery is up to 52.0%.But after reaction carries out 20 hours, catalyst activity just reduces greatly, if for fixed bed reactors, then need frequent regeneration, industrialization is more difficult.
Patent CN103341363A discloses between a kind of orthoresol isomerization production, the fluidized catalyzing method of paracresol, the catalyst wherein related to just comprises molecular sieve series material, but this type of catalyst life is shorter, be not suitable for fixed bed reactors, fluidized-bed process can only be adopted, set complexity, operation easier is large, and production cost is higher.
Patent CN103341363A disclose a kind of orthoresol isomerization produce between, the movable bed catalyst of paracresol and preparation method thereof.What its catalyst adopted is the modified gained of H type ZSM-5 molecular sieve, and equally because catalyst life is too short, be only suitable for and adopt moving bed reaction device, this complex process equipment, automaticity requires higher, and operation easier is large, is difficult to industrialization.
In sum, the catalyst activity of traditional orthoresol isomerization synthesis M-and P-cresols is low, the life-span is short, M-and P-cresols is selective lower, and is not suitable for fixed bed device.
Summary of the invention
Based on this, be necessary low for traditional orthoresol isomerization catalyst activity, the life-span is short, M-and P-cresols is selective lower, and be not suitable for the problem of fixed bed device, there is provided a kind of active high, the life-span is long, M-and P-cresols is selective higher, and is applicable to the orthoresol isomerization catalyst of 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 utilizing orthoresol isomerization catalyst to catalyze and synthesize M-and P-cresols.
A kind of orthoresol isomerization catalyst, in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
Wherein in an embodiment, described binding agent is selected from least one in aluminium oxide and silica.
Wherein in an embodiment, in described H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
A preparation method for orthoresol isomerization catalyst, comprises the following steps:
By H type MCM-41/ZSM-5 composite molecular screen and binding agent mixing, obtain mixture; And
By described mixture kneading, shaping, dry roasting, obtain catalyst, in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
Wherein in an embodiment, described H type MCM-41/ZSM-5 composite molecular screen is prepared by following methods:
Be template with softex kw, add silicon source, aluminium source, alkali source and deionized water and stirring mixing, obtain mixed liquor;
By the pH value of described mixed liquor modulation 10 ~ 11.5,95 ~ 110 DEG C of crystallization 1 ~ 24 hour, obtain sial precursor; And
Described sial precursor is mixed with 4-propyl bromide, 120 ~ 135 DEG C, pH=9 ~ 10, crystallization 48 ~ 96 hours, after filtration, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screen; And
Described Na type MCM-41/ZSM-5 composite molecular screen is mixed with 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solution, the ratio of described Na type MCM-41/ZSM-5 composite molecular screen and described aqueous ammonium nitrate solution is 1:1000g/ml ~ 10:1000g/ml, ion-exchange is carried out 3 ~ 10 hours at 70 ~ 90 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen, in described H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
Wherein in an embodiment, described by described mixture kneading, shaping, dry roasting, obtain in the step of catalyst, the temperature of described roasting is 450 DEG C ~ 600 DEG C;
Described after filtration, washing, dry, roasting, obtain in the step that Na type MCM-41/ZSM-5 compound molecule shines, the temperature of described roasting is 450 DEG C ~ 600 DEG C;
Described after filtration, washing, dry, roasting, obtain in the step that H type MCM-41/ZSM-5 compound molecule shines, the temperature of described roasting is 450 DEG C ~ 600 DEG C.
Wherein in an embodiment, described binding agent is selected from least one in aluminium oxide and silica.
Utilize orthoresol isomerization catalyst to catalyze and synthesize a method for M-and P-cresols, comprise the following steps:
By orthoresol carrier gas exist under with catalyst haptoreaction in fixed bed reactors, obtain M-and P-cresols, in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
Wherein in an embodiment, described by orthoresol under carrier gas exists with catalyst in fixed bed reactors in catalytic step, the condition of described reaction 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 0.1 h
-1~ 4.0h
-1.
Wherein in an embodiment, described by orthoresol under carrier gas exists with catalyst in fixed bed reactors in catalytic step, the condition of described reaction 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.
Above-mentioned orthoresol isomerization catalyst, with silicon source, aluminium source etc. for raw material, in the basic conditions, with softex kw and 4-propyl bromide for template crystallization in two steps forms, this catalyst has greater activity and stability, and the selective of M-and P-cresols can be significantly improved, be suitable for using in fixed bed reactors.
Detailed description of the invention
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below to the specific embodiment of the present invention.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
A kind of orthoresol isomerization catalyst, is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% mass percentage and the binding agent of 5% ~ 35% mass percentage.
Wherein, in H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
Binding agent is selected from least one in aluminium oxide and silica.
In the present embodiment, binding agent is selected from least one in hydrated alumina (such as boehmite or boehmite) and Ludox.
Molecular sieve is the chemical substance with cancellated natural or Prof. Du Yucang.According to the world is pure and the definition of applied chemistry association (IUPAC), porous material can be divided three classes by the difference in aperture: what aperture was less than 2.0nm is micropore, the material with regular micropore canals is called containing Microporous Compounds, as ZSM-5, Y, Bete, MCM-22 etc.; Aperture is mesoporous at 2.0nm ~ 50nm, and the material with ordered mesoporous pore canals structure is called mesoporous material, as MCM-41, MCM-48, SBA-5 etc.; The material that aperture is greater than 50nm is called large pore material.
Micro porous molecular sieve has highly acid and hydrothermal stability, but due to aperture little, major diameter molecule is difficult to enter its duct, and the large molecule reacting generation in duct can not be overflowed fast, often causes side reaction to occur, and its range of application is restricted.Mesopore molecular sieve aperture evenly single, hole wall is thinner, easily collapse under high temperature or hydrothermal condition.
The H type MCM-41/ZSM-5 composite molecular screen that above-mentioned orthoresol isomerization catalyst contains is microporous-mesoporous composite molecular sieve, single micropore, the defect of mesopore molecular sieve can be overcome, bi-material is had complementary advantages, then combines with binding agent, make this catalyst have greater activity and stability.
The preparation method of the orthoresol isomerization catalyst of one embodiment, comprises the following steps:
S110, with softex kw (CTAB) for template, add silicon source, aluminium source, alkali source and deionized water and stirring mixing, obtain mixed liquor.
Wherein, silicon source is selected from least one in Ludox, ethyl orthosilicate and white carbon.Aluminium source is aluminum sulfate, sodium metaaluminate or aluminum nitrate.Alkali source is NaOH.
The addition in above-mentioned aluminium source is converted into Al
2o
3addition, the addition in silicon source is converted into SiO
2addition, then Al
2o
3with SiO
2mol ratio be 0.02 ~ 0.035:1, CTAB and SiO
2mol ratio be 0.08 ~ 0.30:1, NaOH and SiO
2mol ratio be 0.15 ~ 0.2:1.
S120, the pH value of above-mentioned mixed liquor is adjusted to 10 ~ 11.5,95 DEG C ~ 110 DEG C crystallization 1 ~ 24 hour, obtains sial precursor.
Wherein, the method pH value of above-mentioned mixed liquor being adjusted to 10 ~ 11.5 is specially: adopt the sulfuric acid of 30% ~ 50% mass concentration that the pH value of mixed liquor is adjusted to 10 ~ 11.5.
S130, above-mentioned sial precursor mixed with 4-propyl bromide (TPABr), 120 ~ 135 DEG C, pH=9 ~ 10, crystallization 48 ~ 96 hours, after filtration, washing, dry, roasting obtain Na type MCM-41/ZSM-5 composite molecular screen.
Wherein TPABr and SiO
2mol ratio be 0.12 ~ 0.4:1.
Changed in 48 ~ 96 hours by modulation crystallization time, the ratio of Na type MCM-41/ZSM-5 composite molecular screen intermediary hole-micropore can be regulated.
Above-mentioned after filtration, washing, dry, roasting obtain in the step of Na type MCM-41/ZSM-5 composite molecular screen, the temperature of roasting is 450 DEG C ~ 600 DEG C.
S140, above-mentioned Na type MCM-41/ZSM-5 composite molecular screen to be mixed with 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solution, ion-exchange is carried out 3 ~ 10 hours at 70 ~ 90 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen.
Wherein, the ratio of Na type MCM-41/ZSM-5 composite molecular screen and aqueous ammonium nitrate solution is 1:100g/ml ~ 10:1000g/ml.
In H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
Above-mentioned after filtration, washing, dry, roasting, obtain in the step of H type MCM-41/ZSM-5 composite molecular screen, the temperature of roasting is 450 DEG C ~ 600 DEG C.
S150, by above-mentioned H type MCM-41/ZSM-5 composite molecular screen and binding agent mixing, obtain mixture.
Wherein, binding agent is selected from least one in aluminium oxide and silica.
In the present embodiment, binding agent is selected from least one in hydrated alumina (such as boehmite or boehmite) and Ludox.
S160, by said mixture mediate, shaping, dry roasting, obtain catalyst.
Wherein, catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% mass percentage and the binding agent of 5% ~ 35% mass percentage.
In the present embodiment, by said mixture kneading, shaping, dry roasting, obtain in the step of catalyst, the temperature of roasting is 450 DEG C ~ 600 DEG C.Preferably, the temperature of roasting is 550 DEG C.
It should be noted that, above-mentioned H type MCM-41/ZSM-5 composite molecular screen is not limited to the preparation method of above step S110 ~ S140, in other embodiments, H type MCM-41/ZSM-5 composite molecular screen can also adopt additive method prepare or directly buy acquisition.
The preparation method of above-mentioned orthoresol isomerization catalyst is simple, with silicon source, aluminium source etc. for raw material, in the basic conditions, with softex kw and 4-propyl bromide for template crystallization in two steps forms, the catalyst prepared has greater activity and stability, is suitable for using in fixed bed reactors.
Utilize orthoresol isomerization catalyst to catalyze and synthesize a method for M-and P-cresols, comprise the following steps: by orthoresol carrier gas exist under with catalyst haptoreaction in fixed bed reactors, obtain M-and P-cresols.
Wherein, catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% mass percentage and the binding agent of 5% ~ 35% mass percentage.
In H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
Binding agent is selected from least one in aluminium oxide and silica.
Concrete, by orthoresol under carrier gas exists with catalyst catalytic condition in fixed bed reactors be: 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.
Preferably, by orthoresol under carrier gas exists with catalyst catalytic condition in fixed bed reactors be: 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 above-mentioned method utilizing orthoresol isomerization catalytic to synthesize M-and P-cresols, can significantly improve the selective of M-and P-cresols.
It is below specific embodiment.
Embodiment 1
(1) preparation of H type MCM-41/ZSM-5 composite molecular screen
With 17.5g softex kw for template, add the mixing of 60g Ludox, 3.65g aluminum nitrate, 2.28g NaOH and 450g deionized water and stirring, obtain mixed liquor.
Adjust above-mentioned mixed liquor pH value to 11 with the sulfuric acid of mass concentration 50%, 100 DEG C of crystallization 12 hours, obtain sial precursor.
Above-mentioned sial precursor is mixed with 4-propyl bromide, at 125 DEG C, pH=9.5, crystallization 48 hours, after filtration, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screen.
Above-mentioned Na type MCM-41/ZSM-5 composite molecular screen is taken 10g and is dissolved in 1000ml aqueous ammonium nitrate solution (0.5mol/L) mixing, carry out ion-exchange 4 hours at 80 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type MCM-41/ZSM-5 composite molecular screen and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-1.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-1 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 54.5%, and the selective of M-and P-cresols is 98.0%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-1 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 52.8%, and the selective of M-and P-cresols is 98.5%.
Embodiment 2
(1) preparation of H type MCM-41/ZSM-5 composite molecular screen
With 17.5g softex kw for template, add the mixing of 60g Ludox, 3.65g aluminum nitrate, 2.28g NaOH and 450g deionized water and stirring, obtain mixed liquor.
Adjust above-mentioned mixed liquor pH value to 11 with the sulfuric acid of mass concentration 50%, 100 DEG C of crystallization 12 hours, obtain sial precursor.
Above-mentioned sial precursor is mixed with 4-propyl bromide, at 125 DEG C, pH=9.5, crystallization 72 hours, after filtration, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screen.
Above-mentioned Na type MCM-41/ZSM-5 composite molecular screen is taken 10g and is dissolved in 1000ml aqueous ammonium nitrate solution (0.5mol/L) mixing, carry out ion-exchange 4 hours at 80 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type MCM-41/ZSM-5 composite molecular screen and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-2.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-2 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 57.9%, and the selective of M-and P-cresols is 98.8%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-2 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 56.8%, and the selective of M-and P-cresols is 99.2%.
Embodiment 3
(1) preparation of H type MCM-41/ZSM-5 composite molecular screen
With 17.5g softex kw for template, add 60g Ludox, 3.65g aluminum nitrate, 2.28g NaOH and 450g deionized water and add in certain sequence and be uniformly mixed, obtain mixed liquor.
Adjust above-mentioned mixed liquor pH value to 11 with the sulfuric acid of mass concentration 50%, 100 DEG C of crystallization 12 hours, obtain sial precursor.
Above-mentioned sial precursor is mixed with 4-propyl bromide, at 125 DEG C, pH=9.5, crystallization 96 hours, after filtration, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screen.
Above-mentioned Na type MCM-41/ZSM-5 composite molecular screen is taken 10g and is dissolved in 1000ml aqueous ammonium nitrate solution (0.5mol/L) mixing, carry out ion-exchange 4 hours at 80 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type MCM-41/ZSM-5 composite molecular screen and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-3.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-3 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 53.2%, and the selective of M-and P-cresols is 97.2%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-3 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 51.4%, and the selective of M-and P-cresols is 97.9%.
Comparative example 1
(1) preparation of H type MCM-41 molecular sieve
Former for mesostructured material powder is taken 10g and be dissolved in 1000ml aqueous ammonium nitrate solution (0.5mol/L) mixing, carry out the ion-exchange of 4 hours at 80 DEG C, after filtration, washing, drying, obtain H type MCM-41.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type MCM-41 and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-4.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-4 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 40.8%, and the selective of M-and P-cresols is 96.0%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-4 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 35.5%, and the selective of M-and P-cresols is 97.3%.
Comparative example 2
(1) preparation of H type ZSM-5 molecular sieve
Former for ZSM-5 molecular sieve powder is taken 10g and be dissolved in 1000ml aqueous ammonium nitrate solution (0.5mol/L) mixing, carry out the ion-exchange of 4 hours at 80 DEG C, after filtration, washing, drying, obtain H type ZSM-5 molecular sieve.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type ZSM-5 molecular sieve and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-5.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-5 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 60.5%, and the selective of M-and P-cresols is 91.1%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-5 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 40.6%, and the selective of M-and P-cresols is 95.8%.
Comparative example 3
(1) preparation of H type MCM-41/ZSM-5 composite molecular screen
By H type ZSM-5 molecular sieve described in H type MCM-41 described in comparative example 1 and comparative example 2 in 1:1 ratio mechanical mixture, obtain H type MCM-41/ZSM-5 composite molecular screen.
(2) preparation of orthoresol isomerization catalyst
By above-mentioned H type MCM-41/ZSM-5 composite molecular screen and aluminium oxide mixing, mediate, obtain catalyst in 550 DEG C of roastings after shaping, drying, this catalyst is designated as MZM-6.
(3) the catalyzing and synthesizing of M-and P-cresols
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-6 in fixed bed reactors haptoreaction 5 hours, the conversion ratio of orthoresol is 53.2%, and the selective of M-and P-cresols is 93.5%.
By orthoresol under carrier gas exists with above-mentioned catalyst MZM-6 in fixed bed reactors haptoreaction 1000 hours, the conversion ratio of orthoresol is 46.7%, and the selective of M-and P-cresols is 94.2%.
H type MCM-41/ZSM-5 composite molecular screen in embodiment 1 ~ 3 is composited in microcosmic point by weakly acidic MCM-41 molecular sieve and highly acid ZSM-5 molecular sieve, relative to the mechanical impurity of both macroscopic aspect in comparative example 3, its acid centre is evenly distributed, acid intensity is suitable, more be conducive to the carrying out of isomerization reaction, there is higher activity and selectivity, also slow down the carbon distribution speed of acid centre simultaneously.
In addition, due to the micropore-mesopore structure of the H type MCM-41/ZSM-5 composite molecular screen uniqueness in embodiment 1 ~ 3, for H type ZSM-5 molecular sieve independent in comparative example 2, more be conducive to the mass transfer of course of reaction, make reactant can shift out duct in time, reduce the generation of side reaction, simultaneously, also can reduce molecular sieve causes duct to block due to carbon distribution, cover the activated centre of molecular sieve, thus improve the selective of catalyst and service life.
In a word, be used alone the catalyst of H type MCM-41 molecular sieve as orthoresol isomerization reaction, its acid strength is inadequate, reactivity is lower, and is used alone H type ZSM-5 molecular sieve and makes catalyst, then because its acidity is stronger, duct is less, the easy carbon distribution of catalyst and rapid deactivation, catalyst life is shorter, and accessory substance is more.And the H type MCM-41/ZSM-5 composite molecular sieve catalyst set respective advantage of MCM-41 molecular sieve and ZSM-5 molecular sieve, the activity and selectivity of existing higher catalysis orthoresol isomerization reaction, also there is longer service life simultaneously, be suitable for fixed bed reaction technique.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an orthoresol isomerization catalyst, is characterized in that, in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
2. orthoresol isomerization catalyst according to claim 1, is characterized in that, described binding agent is selected from least one in aluminium oxide and silica.
3. orthoresol isomerization catalyst according to claim 1, is characterized in that, in described H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
4. a preparation method for orthoresol isomerization catalyst, is characterized in that, comprises the following steps:
By H type MCM-41/ZSM-5 composite molecular screen and binding agent mixing, obtain mixture; And
Described mixture is mediated, shaping, dry roasting, obtains catalyst, and in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
5. the preparation method of orthoresol isomerization catalyst according to claim 4, is characterized in that, described H type MCM-41/ZSM-5 composite molecular screen is prepared by following methods:
Be template with softex kw, add silicon source, aluminium source, alkali source and deionized water and stirring mixing, obtain mixed liquor;
The pH value of described mixed liquor is adjusted to 10 ~ 11.5,95 ~ 110 DEG C of crystallization 1 ~ 24 hour, obtains sial precursor;
Described sial precursor is mixed with 4-propyl bromide, 120 ~ 135 DEG C, pH=9 ~ 10, crystallization 48 ~ 96 hours, after filtration, washing, dry, roasting, obtain Na type MCM-41/ZSM-5 composite molecular screen; And
Described Na type MCM-41/ZSM-5 composite molecular screen is mixed with 0.5mol/L ~ 2.0mol/L aqueous ammonium nitrate solution, the ratio of described Na type MCM-41/ZSM-5 composite molecular screen and described aqueous ammonium nitrate solution is 1:100g/ml ~ 10:1000g/ml, ion-exchange is carried out 3 ~ 10 hours at 70 ~ 90 DEG C, after filtration, washing, dry, roasting, obtain H type MCM-41/ZSM-5 composite molecular screen, in described H type MCM-41/ZSM-5 composite molecular screen, the mol ratio of Silicified breccias is 30 ~ 45:2.
6. the preparation method of orthoresol isomerization catalyst according to claim 5, is characterized in that, described by described mixture kneading, shaping, dry roasting, obtain in the step of catalyst, the temperature of described roasting is 450 DEG C ~ 600 DEG C;
Described after filtration, washing, dry, roasting, obtain in the step of Na type MCM-41/ZSM-5 composite molecular screen, the temperature of described roasting is 450 DEG C ~ 600 DEG C;
Described after filtration, washing, dry, roasting, obtain in the step of H type MCM-414/ZSM-5 composite molecular screen, the temperature of described roasting is 450 DEG C ~ 600 DEG C.
7. the preparation method of orthoresol isomerization catalyst according to claim 4, is characterized in that, described binding agent is selected from least one in aluminium oxide and silica.
8. utilize orthoresol isomerization catalyst to catalyze and synthesize a method for M-and P-cresols, it is characterized in that, comprise the following steps:
By orthoresol carrier gas exist under with catalyst haptoreaction in fixed bed reactors, obtain M-and P-cresols, in mass percentage, described catalyst is made up of the H type MCM-41/ZSM-5 composite molecular screen of 65% ~ 95% and the binding agent of 5% ~ 35%.
9. the method utilizing orthoresol isomerization catalyst to catalyze and synthesize M-and P-cresols according to claim 8, it is characterized in that, described by orthoresol under carrier gas exists with catalyst in fixed bed reactors in catalytic step, the condition of described reaction is specially: temperature is 300 DEG C ~ 450 DEG C, pressure is 0.2MPa ~ 3.5MPa, and the mass space velocity of orthoresol is 0.1h
-1~ 4.0h
-1.
10. the method utilizing orthoresol isomerization catalyst to catalyze and synthesize M-and P-cresols according to claim 8, it is characterized in that, described by the mixture of orthoresol and phenol under carrier gas exists with catalyst in fixed bed reactors in catalytic step, the condition of described reaction is specially: temperature is 330 DEG C ~ 390 DEG C, pressure is 0.5MPa ~ 2.5MPa, and the mass space velocity of orthoresol is 0.5h
-1~ 2.5h
-1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
| 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 |
| CN113351243A (en) * | 2021-06-21 | 2021-09-07 | 山西大学 | Catalyst for producing m-cresol from o-cresol by isomerization and preparation method thereof |
| CN113731476A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Solid acid catalyst and method for producing m-cresol |
| CN114053962A (en) * | 2021-11-08 | 2022-02-18 | 大连凯飞化学股份有限公司 | Fluidized bed reaction system and method for in-situ catalytic synthesis of thymol |
| CN115155650A (en) * | 2022-08-01 | 2022-10-11 | 浙江医药股份有限公司新昌制药厂 | Catalyst and preparation method and application thereof |
| CN115445653A (en) * | 2022-09-01 | 2022-12-09 | 宁夏派可威生物科技有限公司 | Preparation process of cresol isomerization catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4691063A (en) * | 1986-06-16 | 1987-09-01 | Uop Inc. | Isomerization of cresols |
| US20130165315A1 (en) * | 2011-12-27 | 2013-06-27 | King Fahd University Of Petroleum And Minerals | Method of forming a hydrocarbon cracking catalyst |
| CN103342629A (en) * | 2013-07-18 | 2013-10-09 | 北京旭阳化工技术研究院有限公司 | Fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol |
| CN103341363A (en) * | 2013-07-25 | 2013-10-09 | 北京旭阳化工技术研究院有限公司 | Moving-bed catalyst for preparing m-cresol and p-cresol from o-cresol by isomerization and preparation method thereof |
| CN103723741A (en) * | 2013-12-19 | 2014-04-16 | 大同煤矿集团有限责任公司 | Method for synthesizing ZSM-5/MCM-41 composite molecular sieve |
| CN103861637A (en) * | 2014-04-02 | 2014-06-18 | 中国石油大学(华东) | Synthesis method of ZSM-5 @ MCM-41 core-shell composite molecular sieve |
| CN104058421A (en) * | 2014-06-09 | 2014-09-24 | 罗小林 | Preparation method of microporous-mesoporous ZSM-5/MCM-41 composite molecular sieve with core-shell structure |
-
2015
- 2015-06-17 CN CN201510334647.2A patent/CN104923293B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4691063A (en) * | 1986-06-16 | 1987-09-01 | Uop Inc. | Isomerization of cresols |
| US20130165315A1 (en) * | 2011-12-27 | 2013-06-27 | King Fahd University Of Petroleum And Minerals | Method of forming a hydrocarbon cracking catalyst |
| CN103342629A (en) * | 2013-07-18 | 2013-10-09 | 北京旭阳化工技术研究院有限公司 | Fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol |
| CN103341363A (en) * | 2013-07-25 | 2013-10-09 | 北京旭阳化工技术研究院有限公司 | Moving-bed catalyst for preparing m-cresol and p-cresol from o-cresol by isomerization and preparation method thereof |
| CN103723741A (en) * | 2013-12-19 | 2014-04-16 | 大同煤矿集团有限责任公司 | Method for synthesizing ZSM-5/MCM-41 composite molecular sieve |
| CN103861637A (en) * | 2014-04-02 | 2014-06-18 | 中国石油大学(华东) | Synthesis method of ZSM-5 @ MCM-41 core-shell composite molecular sieve |
| CN104058421A (en) * | 2014-06-09 | 2014-09-24 | 罗小林 | Preparation method of microporous-mesoporous ZSM-5/MCM-41 composite molecular sieve with core-shell structure |
Non-Patent Citations (1)
| Title |
|---|
| LIMIN HUANG ET AL.: "Investigation of Synthesizing MCM-41/ZSM-5 Composites", 《J. PHYS. CHEM. B》 * |
Cited By (10)
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|---|---|---|---|---|
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
| CN107879900B (en) * | 2017-12-22 | 2024-05-14 | 中触媒新材料股份有限公司 | Process method for separating and purifying cresol mixed isomer |
| 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 |
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| CN113731476A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Solid acid catalyst and method for producing m-cresol |
| CN113731476B (en) * | 2021-06-23 | 2023-10-03 | 浙江环化科技有限公司 | Method for producing m-cresol |
| CN114053962A (en) * | 2021-11-08 | 2022-02-18 | 大连凯飞化学股份有限公司 | Fluidized bed reaction system and method for in-situ catalytic synthesis of thymol |
| CN115155650A (en) * | 2022-08-01 | 2022-10-11 | 浙江医药股份有限公司新昌制药厂 | Catalyst and preparation method and application thereof |
| 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 |
| CN115445653A (en) * | 2022-09-01 | 2022-12-09 | 宁夏派可威生物科技有限公司 | Preparation process of cresol isomerization catalyst |
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