CN107986295A - A kind of siliceous molecular sieve and preparation method thereof - Google Patents
A kind of siliceous molecular sieve and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to catalytic field, specifically provides a kind of siliceous molecular sieve and preparation method thereof, this method includes：(1) silicon source, group VIII source metal and structure directing agent are hydrolyzed to obtain hydrolysis material；(2) the hydrolysis material is subjected to crystallization；Wherein, step (1) carries out in the presence of organic phosphorus compound and/or before step (2) progress, and the crystallization is carried out again after the hydrolysis material is mixed with organic phosphorus compound.Siliceous molecular sieve prepared by method using the present invention can be applied to every field, such as dehydration, selective dehydrogenation reaction, alkylated reaction, denitration reaction (reduction), isomerization reaction etc..The siliceous molecular sieve of the present invention, which is used for catalytic and dehydration reaction, has the advantages that feed stock conversion is high, target product selectivity is high.The siliceous molecular sieve of the present invention is used for cyclohexyl hydroperoxide catalytic decomposition, without adding extra alkaline reagent, reaction effect of the high alcohol ketone than, high alcohol ketone selectivity can be obtained at a lower temperature, it is very high in industrial application value.
Description
Technical field
The present invention relates to a kind of siliceous molecular sieve and preparation method thereof.
Background technology
Cyclohexanone is important basic chemical industry raw material, and it is important that it has been used for caprolactam, adipic acid and 6-caprolactone etc.
The production of chemical products.According to statistics, ended for the end of the year 2015, the production capacity of China's cyclohexanone has reached 3,650,000 tons.China cyclohexanone master
To be produced by cyclohexane oxidation and cyclohexene hydrating process, and the production capacity accounting of cyclohexane oxidation is up to 63%.
Existing cyclohexane oxidation technique mainly includes cyclohexane oxidation, cyclohexyl hydroperoxide decomposes and cyclohexanol dehydrogenation three
A process.Although dehydrogenation technology for cyclohexanol relative maturity is stablized, the side reaction of cyclohexane oxidation technique is more, hexamethylene conversion
Rate be not higher than 4%, cyclohexyl hydroperoxide decompose then by alcohol ketone yield it is low (<88%), three wastes discharge amount is big and handles difficulty etc.
Problem restricts.
Cyclohexyl hydroperoxide decomposition is the important step that oxidizing process prepares cyclohexanone technique, and existing process is typically in alkali
Property under the conditions of (38%~42% NaOH solution), micro soluble cobalt catalysis cyclohexyl hydroperoxide resolve into cyclohexanol
And cyclohexanone.Under the process conditions, cyclohexanol and cyclohexanone can be further condensed, so as to reduce alcohol ketone yield；Cobalt salt can not return
Receive, and the problems such as precipitating, line clogging may be triggered can be formed with a small amount of organic acid reaction in cyclohexyl hydroperoxide solution；
1~1.2 ton of inorganic alkali wasteliquid can be produced by often producing 1 ton of cyclohexanone, and the waste liquid contains substantial amounts of organic matter, the difficult recycling of organic matter
Recycling, wastewater treatment are difficult, of high cost.
To solve the problems, such as that inorganic base/cobalt salt system exists, people mainly develop heterogeneous catalysis material.Du Pont
Company was once developed using activated alumina, silica, titanium dioxide or activated carbon as carrier, with iron oxide, cobalt oxide, nickel oxide,
Manganese oxide, niobium oxide or noble metal are support materials for catalysts (US 2851496, US 4503257, the WO in activated centre
9809931、US 4720592)；BASF AG is then respectively using molecular sieve and iron oxide, cobalt oxide, nickel oxide as catalyst
Carrier and active component, and have studied the cyclohexyl hydroperoxide decomposability (US 4491637) of loaded catalyst；Supreme Being Si
Mann is then mainly to the support type using chromium oxide, copper chromium composite oxides, phthalocyanine or purine metallic compound as active component
Catalyst is developed (US 3941845, US 3987101, US 4042630, CN 89108142.9, CN 91103225).
In addition, hetero-atom molecular-sieve, including Cr-AFI (Sheldon R A, Chen J D, Dakka J, et al.Studies in
Surface Science and Catalysis,1994,82:515-529.)、Cr-MFI(Chapus T,Tuel A,Taarit
Y B,et al.Zeolites,1994,14(5):349-355.), Co-Cr-TUD (Li Li rosy clouds University Of Xiangtan Master's thesis,
2016.), also it is used for the decomposition research of cyclohexyl hydroperoxide.
Although more than, the active force of metal oxide and carrier is weaker, and the stability of support materials for catalysts has much room for improvement；
In loaded catalyst, the content of metal oxide it is higher (>1% mass fraction), this is difficult to ensure that active component can uniformly divide
Cloth；AFI and the pore size of MFI structure are not more than 0.55nm, and the molecular dimension of cyclohexyl hydroperoxide is about 0.74nm, and two
Cr activated centres in kind molecular sieve are difficult relatively low with CHHP effects, the effective rate of utilization in the activated centre of hetero-atom molecular-sieve；Though
Right mesoporous TUD has larger pore passage structure, but its hole wall is amorphous species, its hydrothermal stability is unsatisfactory.
In summary analyze, to solve the problems, such as that existing homogeneous catalysis cyclohexyl hydroperoxide decomposition technique exists, multiphase
The exploitation of catalysis material is crucial, should further be furtherd investigate to prepare active component high degree of dispersion, activated centre is close to
Property it is good and with preferable hydrothermal stability cyclohexyl hydroperoxide decomposition catalyst.
The content of the invention
It is prepared it is an object of the invention to provide a kind of preparation method of new siliceous molecular sieve, and by this method
Siliceous molecular sieve.
In order to realize object defined above, according to the first aspect of the invention, the present invention provides a kind of system of siliceous molecular sieve
Preparation Method, this method include：
(1) silicon source, group VIII source metal and structure directing agent are hydrolyzed to obtain hydrolysis material；
(2) the hydrolysis material is subjected to crystallization；
Wherein, step (1) carries out in the presence of organic phosphorus compound and/or before step (2) progress, by the hydrolysate
Material carries out the crystallization again after being mixed with organic phosphorus compound.
According to the second aspect of the invention, the present invention provides the siliceous molecular sieve being prepared by preceding method.
Siliceous molecular sieve prepared by method using the present invention is with specific surface area is big, active center distribution is uniform and can connect
Nearly property is good, surface hydrophilicity is strong, can produce selective absorption, activity stability and hydrothermal stability to alcohol, ketone, peroxide etc.
The excellent physicochemical characteristic such as good.
Siliceous molecular sieve prepared by method using the present invention can be applied to every field, such as dehydration, select
Property dehydrogenation reaction, alkylated reaction, denitration reaction (reduction), isomerization reaction etc..
The siliceous molecular sieve of the present invention, which is used for catalytic and dehydration reaction, has feed stock conversion height, target product selectivity height etc.
Advantage.
The siliceous molecular sieve of the present invention is catalytically decomposed for cyclohexyl hydroperoxide, without adding extra alkalescence examination
Agent, can obtain reaction effect of the high alcohol ketone than, high alcohol ketone selectivity, at a lower temperature in industrial application value very
It is high.
It is shown below：
Cyclohexyl hydroperoxide is the primary product of cyclohexane selectivity hydrogenation, and product, which is catalytically decomposed, in it mainly includes hexamethylene
Alcohol and cyclohexanone.
When selectively producing cyclohexanone, although energy consumption relative reduction, molecular hydrogen resource conversion generation water, hydrogen resource
Utilization rate it is relatively low, and improve the load of follow-up water treatment facilities.
And when selectively producing cyclohexanol, cyclohexanol generates cyclohexanone by dehydrogenation, and resulting hydrogen is recyclable
For benzene hydrogenation process, the effective rate of utilization of raising hydrogen resource.I.e. the method according to the invention can greatly improve hydrogen atom
Utilization rate, is to provide a kind of feasibility option in industrializing implementation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of siliceous molecular sieve, this method includes：
(1) silicon source, group VIII source metal and structure directing agent are hydrolyzed to obtain hydrolysis material；
(2) the hydrolysis material is subjected to crystallization；
Wherein, step (1) carries out in the presence of organic phosphorus compound and/or before step (2) progress, by the hydrolysate
Material carries out the crystallization again after being mixed with organic phosphorus compound.
In the present invention, the organic phosphorus compound refers to the organic compound containing phosphorus.
Siliceous molecular sieve prepared by method using the present invention is with specific surface area is big, active center distribution is uniform and can connect
Nearly property is good, surface hydrophilicity is strong, can produce selective absorption, activity stability and hydrothermal stability to alcohol, ketone, peroxide etc.
The excellent physicochemical characteristic such as good.
Siliceous molecular sieve prepared by method using the present invention can be applied to every field, such as dehydration, select
Property dehydrogenation reaction, alkylated reaction, denitration reaction (reduction), isomerization reaction etc..
According to preceding solution, the purpose of the present invention, for the present invention, preferably described organic phosphorus compound can be achieved
Molar ratio with silicon source is P：SiO2=(0.001-0.5)：1, more preferably P：SiO2=(0.1-0.3)：1.It is possible thereby to improve
The performance of the siliceous molecular sieve, such as urging for its catalyst for being used to be catalytically decomposed as cyclohexyl hydroperoxide can be improved
Change decomposability, greatly improve alcohol ketone ratio, and alcohol ketone selectivity is high.
A preferred embodiment of the invention, this method include：
(1) silicon source, group VIII source metal, Part I organic phosphorus compound and structure directing agent are hydrolyzed to obtain
Hydrolyze material；
(2) crystallization is carried out after the hydrolysis material is mixed with Part II organic phosphorus compound.According to foregoing step
It is rapid to carry out, the performance of the siliceous molecular sieve can be further improved, such as it can be improved and be used for as cyclohexyl peroxidating
The catalytic decomposition performance for the catalyst that hydrogen catalysis decomposes, greatly improves alcohol ketone ratio, and alcohol ketone selectivity is high.
With the method for the invention it is preferred to counted by 100 weight % of total dosage of the organic phosphorus compound, Part I
The dosage of organic phosphorus compound is 10-90 weight %, and the dosage of Part II organic phosphorus compound is 10-90 weight %；It is more excellent
The dosage for selecting Part I organic phosphorus compound is 30-40 weight %, and the dosage of Part II organic phosphorus compound is 60-70 weights
Measure %.
With the method for the invention it is preferred to the condition that the hydrolysis material is mixed with organic phosphorus compound includes：Temperature is
60-100 DEG C, be preferably 70-90 DEG C.It is possible thereby to further improve the performance of the siliceous molecular sieve, such as it can be improved
Catalytic decomposition performance for the catalyst being catalytically decomposed as cyclohexyl hydroperoxide, greatly improves alcohol ketone ratio, and alcohol ketone selects
Selecting property height.
The method according to the invention, the condition that more preferably described hydrolysis material is mixed with organic phosphorus compound include：Time
It is preferably 2-4h for 1-10h.
The method according to the invention, group VIII metal may be incorporated for the present invention, for the preferred group VIII of the present invention
Metal is the one or more in cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, more preferably cobalt.
With the method for the invention it is preferred to silicon source, group VIII source metal and structure directing agent are hydrolyzed in silane
Carry out and/or be blended in the hydrolysis material in the presence of silylating reagent with organic phosphorus compound to carry out in the presence of change reagent；
More preferably described silicon source and the molar ratio of silylating reagent are SiO2：Silylating reagent=1：(0.001-0.1), is preferably SiO2：
Silylating reagent=1：(0.01-0.06).
A preferred embodiment of the invention, this method include：(1) by silicon source, group VIII source metal, first
Part organic phosphorus compound is hydrolyzed to obtain hydrolysis material with structure directing agent；
(2) crystallization is carried out after mixing hydrolysis material, Part II organic phosphorus compound and the silylating reagent.
Preferably, counted by 100 weight % of total dosage of the organic phosphorus compound, Part I organic phosphorus compound
Dosage is 10-90 weight %, and the dosage of Part II organic phosphorus compound is 10-90 weight %, and the silicon source is tried with silanization
The molar ratio of agent is SiO2：Silylating reagent=1：(0.001-0.1)；It is preferred that the dosage of Part I organic phosphorus compound is
30-40 weight %, the dosage of Part II organic phosphorus compound are 60-70 weight %, and the silicon source and silylating reagent rub
Your ratio is SiO2：Silylating reagent=1：(0.01-0.06).
According to the present invention, the silylating reagent is preferably the compound of below formula：
R in formula (I)1、R2、R3And R4It is each independently halogen, alkyl, alkoxy, aromatic radical or amido, and at least one
For alkyl, alkoxy, aromatic radical or amido；The carbon number of the alkyl, alkoxy and amido is each independently 1-18；It is excellent
The silylating reagent of choosing is dimethyldichlorosilane, methyl trichlorosilane, trim,ethylchlorosilane, pungent four silica of methyl of 1,7- dichloros
Alkane, [3- trimethoxy silicon propyl group] dimethyloctadecylammonium ammonium bromide, N- phenyl -3- TSL 8330s, phenyl three
Ethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, methyltriethoxysilane, tert-butyl chloro-silicane,
At least one of hexadecyl trimethoxy silane and octyltri-ethoxysilane；More preferably there is suitably reaction to live
Phenyl triethoxysilane, hexamethyldisilazane, hexamethyldisiloxane and the methyltriethoxy silane of property and molecular dimension
At least one of alkane.
According to the present invention, optional wider range of the organic phosphorus compound, for the present invention, preferably described organic phosphatization
Compound is the one or more in such as following formula (II), formula (III) and formula (IV),
Wherein, the R in formula (II), formula (III) and formula (IV) is respectively the one or more in alkyl, aryl and amido；
R preferably in formula (II), formula (III) and formula (IV) is respectively the straight chained alkyl of C1-C18, the branched alkyl of C3-C18, C6-
One or more in the aryl and amido of C16.
According to the preferred embodiment of the present invention, preferably described organic phosphorus compound for triethyl phosphate, tricresyl phosphate propyl ester,
Tributyl phosphate, three iso-butyl ester of phosphoric acid, tri hexyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate and tricresyl phosphate
One or more in (2- chloropropyls) ester.
A preferred embodiment of the invention, Part I organic phosphorus compound are triphenyl phosphate, second
It is tricresyl phosphate (2- chloropropyls) ester to divide organic phosphorus compound.
According to the present invention, the silicon source can be that synthesis siliceous molecular sieve well-known to those skilled in the art is commonly used
Silicon source, the present invention has no particular limits it, for example, the silicon source can be estersil (organosilicon acid esters), it is solid silicone, white
At least one of carbon black and Ludox；In order to avoid the trivalent heteroatoms such as the hetero atom in silicon source such as boron or aluminium are to siliceous molecule
The issuable influence of crystallization of sieve, the silicon source are preferably the estersil that dioxide-containing silica is high and impurity content is few, solid
At least one of silica gel and white carbon；More preferably estersil, wherein, shown in the general formula such as following formula (V) of described estersil：
In formula (V), R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R1、R2、R3And R4Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or tertiary fourth
Base, wherein it is preferred that R1、R2、R3And R4It is methyl or ethyl.
The method according to the invention, the silicone grease are, for example, methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and positive silicon
One or more in acid butyl ester.Specifically, the silicone grease can be positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four
One or more in four N-butyl of n-propyl and positive silicic acid.
According to the present invention, the structure directing agent used in the step (1) is commonly used when can be synthesis siliceous molecular sieve
Structure directing agent, the present invention it is had no particular limits, such as the structure directing agent can be quaternary ammonium base, aliphatic amine and
At least one of aliphatic hydramine；Wherein, described quaternary ammonium base can be organic level Four ammonium alkali, and described aliphatic amine can be with
For NH3In at least one hydrogen substituted by aliphatic alkyl (such as alkyl) after the compound that is formed, described aliphatic hydramine can
Think various NH3In at least one hydrogen by the compound that is formed after aliphatic group (such as alkyl) substitution of hydroxyl.
Specifically, the structure directing agent can be the fat that quaternary ammonium base, the general formula VII represented selected from general formula VI is represented
At least one of aliphatic hydramine that race's amine and general formula VIII are represented.
In Formula IV, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R1、R2、R3And R4Each can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or/
And the tert-butyl group.
R5(NH2)n(Formula VII)
In Formula VII, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6
Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or/and sub- n-hexyl.
(HOR6)mNH(3-m)(Formula VIII)
In Formula VIII, m R6Can be identical or different, it is respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub
And C3-C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and/or sub- normal-butyl；M is 1,2 or 3.
Preferably, the structure directing agent described in step (1) can be tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, four
Propyl group ammonium hydroxide (includes the various isomers of tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl hydrogen-oxygen
Change ammonium), tetrabutylammonium hydroxide (include the various isomers of tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and four different
Butyl ammonium hydroxide)；Further, the structure directing agent is tetrapropylammonium hydroxide.
In the present invention, the exemplary advantage for illustrating the present invention as template using tetrapropylammonium hydroxide.
The method according to the invention, the group VIII source metal are water miscible group VIII metallic compound；Such as
When the group VIII metal is cobalt, the metallic compound for cobalt trifluoride, six cyano cobalt acid potassium, hexanitro cobalt acid sodium,
In acetylacetone cobalt, six amino cobalt chlorides, three (2,4- pentanedionate) cobalts, two (pentamethylcyclopentadiene base) hexafluorophosphoric acid cobalts
It is one or more.
According to the present invention, the condition of the hydrolysis can be the routine hydrolysis condition of this area, for this without particular/special requirement
Invention, mol ratio of the condition including material of selective hydrolysis is SiO2：Structure directing agent：Group VIII metal：H2O=
1：(0.001-5)：(0.0001-0.1)：(5-400), is preferably SiO2：Structure directing agent：Group VIII metal：H2O=1：
(0.05-0.1)：(0.0005-0.01)：(200-400).
According to the present invention, the condition of the hydrolysis can be the routine hydrolysis condition of this area, for this without particular/special requirement
Invention, it is 10-120 DEG C that the condition of selective hydrolysis, which includes temperature, is preferably 30-60 DEG C.
The time of hydrolysis can carry out condition according to hydrolysis temperature, can be preferably generally 4-10h with selected as 1-24h.
According to the present invention, the condition of crystallization can be the conventional crystallization condition of this area, preferably include：In confined conditions
Crystallization, temperature are 110-230 DEG C, are preferably 130-200 DEG C.
The time of crystallization can be adjusted according to the time, for preferably crystallization time of the invention for 1-240 it is small when, preferably
For 10-28h.
The method according to the invention, the hydrolysis carry out in the presence of aqueous solvent, and the species of the aqueous solvent can be with
For the conventional selection of this area, various aqueous solvents may be incorporated for realizing the present invention, as long as the water wherein in aqueous solvent
It can meet that silicon source generates the condition of siliceous molecular sieve in crystallization process.The solvent is preferably water, also can be according to needs
Other cosolvents are added, to this present invention without specific requirement, this is not described in detail here.It should be noted that aqueous solvent can
To arise directly from the solvent content of other material solutions, such as the solvent portion of structure directing agent aqueous solution can be directed to
Point；Can also directly it add, need not if the solvent content of other aqueous solution of raw material disclosure satisfy that the requirement that feeds intake of aqueous solvent
Aqueous solvent is added again, if not satisfied, then needing additionally to add aqueous solvent.
In the present invention, to the pressure of crystallization without particular/special requirement, crystallization can be carried out at autogenous pressures.
With the method for the invention it is preferred to this method further includes：The filtering of crystallization products therefrom, washing are obtained into solid, will
Roasted after obtained solid is dry or moist.
In the present invention, optional wider range of the condition of the drying, is specifically referred to prior art progress.For this
Invention, the condition of preferably described drying include：Temperature for room temperature to 200 DEG C, more preferably 80-120 DEG C；Time is 1-24h, excellent
Elect 2-10h as.
In the present invention, optional wider range of the condition of the roasting, for the condition bag of the preferably roasting of the invention
Include：The temperature of roasting is 300-800 DEG C, is preferably 450-550 DEG C；The time of roasting is 2-12h, is preferably 2-4h.
The present invention provides the siliceous molecular sieve being prepared according to preparation method of the present invention.
The present invention provides the application of siliceous molecular sieve of the invention in cyclohexyl hydroperoxide catalytic decomposition.
The present invention provides a kind of method of cyclohexyl hydroperoxide catalytic decomposition, this method includes：By cyclohexyl peroxide
Change hydrogen to contact with catalyst, the catalyst contains siliceous molecular sieve of the present invention.
The method according to the invention, as long as siliceous molecular sieve of the catalyst containing the present invention, preferably described to urge
The content of siliceous molecular sieve of the invention is more than 50 weight % in agent, and more preferably content is 60-100 weight %.In this hair
What is used in bright specific embodiment is that the content of the siliceous molecular sieve of the present invention is the catalyst of 100 weight %, but this is simultaneously
It is not so limited the scope of the present invention.Catalyst composition when content herein refers to being free of carrier.
When the catalyst is formed body, the catalyst further includes carrier, wherein, carrier can be Al2O3、ZnO、
MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE La, Ce, Y or Nd etc.).
In the present invention, in the catalyst, in addition to including siliceous molecular sieve of the present invention, it is normal that other can also be contained
It is used for the catalyst of cyclohexyl hydroperoxide catalytic decomposition.
A kind of preferred embodiment according to the present invention, preferably described catalyst is this hair that content is 100 weight %
The bright siliceous molecular sieve, the condition of the contact include：Temperature is 80-100 DEG C, preferably 85-95 DEG C.
The weight ratio of catalyst and cyclohexyl hydroperoxide is (0.001-0.5)：1, be preferably (0.01-0.2)：1, it is more excellent
Elect as (0.02-0.1)：1.
The present invention is further illustrated for following embodiment, but the content being not intended to limit the present invention.Implement
All reagents used are commercially available chemically pure reagent in example.
In embodiment, using water as aqueous solvent, in mixed process, if other feed intake, contained water disclosure satisfy that pair
The requirement that feeds intake of water, then need not add water, if not satisfied, being then added as needed on water.
Embodiment 1
(1) by tetraethyl orthosilicate, cobalt trifluoride, tricresyl phosphate propyl ester, tetrapropylammonium hydroxide aqueous solution, (concentration is 25 weights
Amount %) it is hydrolyzed to obtain hydrolysis material；The temperature of hydrolysis is 30 DEG C, time 10h；
(2) will the hydrolysis material, tricresyl phosphate propyl ester and methyltriethoxysilane be transferred to after mixing in crystallizing kettle into
Row crystallization, wherein, the condition of mixing includes：Temperature is 70 DEG C, and time 4h, the condition of crystallization includes：It is spontaneous under confined conditions
Crystallization under pressure, temperature are 160 DEG C, time 24h；
Wherein, the dosage in step (1) with the tricresyl phosphate propyl ester in step (2) is respectively the 30 of the total dosage of tricresyl phosphate propyl ester
Weight %, 70 weight %；
The mol ratio of each material is SiO2：Structure directing agent：Group VIII metal：H2O=1：0.05：0.005：
200, SiO2：Molar ratio=1 of silylating reagent：0.03, P：SiO2Molar ratio=0.1：1；
By the product filtering after crystallization, dry (110 DEG C drying 60 minutes), roast (in 550 DEG C of temperature in air atmosphere
Roast 3 it is small when) obtain siliceous molecular sieve C1.
Embodiment 2
(1) by positive silicic acid orthocarbonate, hexanitro cobalt acid sodium, trioctyl phosphate, tetrapropylammonium hydroxide aqueous solution, (concentration is
25 weight %) it is hydrolyzed to obtain hydrolysis material；The temperature of hydrolysis is 50 DEG C, time 6h；
(2) will the hydrolysis material, trioctyl phosphate and phenyl triethoxysilane be transferred to after mixing in crystallizing kettle into
Row crystallization, wherein, the condition of mixing includes：Temperature is 80 DEG C, and time 3h, the condition of crystallization includes：It is spontaneous under confined conditions
Crystallization under pressure, temperature are 130 DEG C, time 28h；
Wherein, the dosage in step (1) with the trioctyl phosphate in step (2) is respectively the 35 of the total dosage of trioctyl phosphate
Weight %, 65 weight %；
The mol ratio of each material is SiO2：Structure directing agent：Group VIII metal：H2O=1：0.06：0.008：
300, SiO2：Molar ratio=1 of silylating reagent：0.05, P：SiO2Molar ratio=0.2：1；
By the product filtering after crystallization, dry (110 DEG C drying 60 minutes), roast (in 550 DEG C of temperature in air atmosphere
Roast 3 it is small when) obtain siliceous molecular sieve C2.
Embodiment 3
(1) by positive four N-butyl of silicic acid, three (2,4- pentanedionates) cobalts, tricresyl phosphate (2- chloropropyls) ester, tetrapropyl hydrogen-oxygen
Change aqueous ammonium (concentration is 25 weight %) to be hydrolyzed to obtain hydrolysis material；The temperature of hydrolysis is 60 DEG C, time 4h；
(2) crystallization is transferred to after mixing hydrolysis material, tricresyl phosphate (2- chloropropyls) ester and the hexamethyldisilazane
Crystallization is carried out in kettle, wherein, the condition of mixing includes：Temperature is 90 DEG C, and time 2h, the condition of crystallization includes：Confined condition
Crystallization under lower self-generated pressure, temperature are 200 DEG C, time 10h；
Wherein, the dosage in step (1) with the trioctyl phosphate in step (2) is respectively the 40 of the total dosage of trioctyl phosphate
Weight %, 60 weight %；
The mol ratio of each material is SiO2：Structure directing agent：Group VIII metal：H2O=1：0.1：0.01：
400, SiO2：Molar ratio=1 of silylating reagent：0.04, P：SiO2Molar ratio=0.3：1；
By the product filtering after crystallization, dry (110 DEG C drying 60 minutes), roast (in 550 DEG C of temperature in air atmosphere
Roast 3 it is small when) obtain siliceous molecular sieve C3.
Embodiment 4
Method according to embodiment 1 prepares siliceous molecular sieve C4, unlike, tricresyl phosphate propyl ester is all in step (1)
Add.
Embodiment 5
Method according to embodiment 1 prepares siliceous molecular sieve C5, unlike, tricresyl phosphate propyl ester is all in step (2)
Add.
Embodiment 6
Method according to embodiment 1 prepares siliceous molecular sieve C6, unlike, methyltriethoxysilane is in step (1)
Middle addition.
Embodiment 7
Method according to embodiment 1 prepares siliceous molecular sieve C7, unlike, the temperature of mixing is 60 DEG C in step (2),
Time is 10h.
Embodiment 8
Method according to embodiment 1 prepares siliceous molecular sieve C8, unlike, the temperature of mixing is 100 in step (2)
DEG C, time 1h.
Embodiment 9
Method according to embodiment 1 prepares siliceous molecular sieve C9, unlike, in step (1) with the phosphoric acid in step (2)
The dosage of three propyl ester is respectively 70 weight %, 30 weight % of the total dosage of tricresyl phosphate propyl ester.
Embodiment 10
Method according to embodiment 1 prepares siliceous molecular sieve C10, unlike, in step (1) with the phosphorus in step (2)
The dosage of sour three propyl ester is respectively 20 weight %, 80 weight % of the total dosage of tricresyl phosphate propyl ester.
Embodiment 11
Method according to embodiment 1 prepares siliceous molecular sieve C11, unlike, P：SiO2Molar ratio=0.4：1.
Embodiment 12
Method according to embodiment 1 prepares siliceous molecular sieve C12, unlike, organic phosphorus compound is phosphorus in step (1)
Triphenyl phosphate ester, organic phosphorus compound is tricresyl phosphate (2- chloropropyls) ester in step (2).
Embodiment 13
Method according to embodiment 1 prepares siliceous molecular sieve C13, unlike, group VIII metallic compound is nitric acid
Nickel.
Embodiment 14
Method according to embodiment 1 prepares siliceous molecular sieve C14, unlike, silylating reagent is fert-butyidimethylsilyl
Chlorosilane.
Test case
The siliceous molecular sieve that this test case is used to illustrate to obtain by method provided by the invention is used for cyclohexyl peroxidating
The reaction effect of hydrogen catalysis decomposition reaction.
Sample prepared by above-described embodiment 1-14 is used to be catalyzed cyclohexyl hydroperoxide decomposition, by cyclohexyl peroxidating
Hydrogen is contacted with catalyst, and the temperature of contact is 85 DEG C, time 0.5h, and the weight ratio of catalyst and cyclohexyl hydroperoxide is
0.01：1, the result is shown in table 1 below.
Wherein, products therefrom is measured on Agilent6890N chromatographs using HP-5 capillary columns (30m × 0.25mm)
Each product distribution.
The hexamethylene of molal quantity/addition of the cyclohexyl hydroperoxide of cyclohexylhydroperoxconversion conversion rate (%)=participation reaction
The molal quantity of base hydrogen peroxide.
The cyclohexyl peroxide of alcohol ketone selectivity (%)=(molal quantity of molal quantity+cyclohexanone of cyclohexanol)/participation reaction
Change the molal quantity of hydrogen.
Molal quantity of the alcohol ketone than molal quantity/cyclohexanone of=cyclohexanol
Wherein, the molal quantity that the molal quantity=cyclohexyl hydroperoxide for the cyclohexyl hydroperoxide for participating in reacting feeds intake-
To reaction mixture in remaining cyclohexyl hydroperoxide molal quantity.
Table 1
From the results shown in Table 1, the catalytic activity for the siliceous molecular sieve that the method according to the invention is prepared is high,
Si molecular sieves containing cobalt, for the catalytic decomposition of cyclohexyl hydroperoxide, at 85 DEG C, 0.5h is available more than 99% hexamethylene
Base hydrogen peroxide conversion, more than 95% alcohol ketone selectivity, and alcohol ketone ratio are more than 2.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of siliceous molecular sieve, it is characterised in that this method includes：
(1) silicon source, group VIII source metal and structure directing agent are hydrolyzed to obtain hydrolysis material；
(2) the hydrolysis material is subjected to crystallization；
Wherein, step (1) carries out in the presence of the organic phosphorus compound and/or before step (2) progress, by the hydrolysis material with
The crystallization is carried out again after organic phosphorus compound mixing.
2. preparation method according to claim 1, wherein, the molar ratio of the organic phosphorus compound and silicon source is P：SiO2
=(0.001-0.5)：1, it is preferably P：SiO2=(0.1-0.3)：1.
3. preparation method according to claim 1 or 2, wherein, this method includes：
(1) silicon source, group VIII source metal, Part I organic phosphorus compound and structure directing agent are hydrolyzed and are hydrolyzed
Material；
(2) crystallization is carried out after the hydrolysis material is mixed with Part II organic phosphorus compound.
4. preparation method according to claim 3, wherein, using total dosage of the organic phosphorus compound as 100 weight %
Meter, the dosage of Part I organic phosphorus compound is 10-90 weight %, and the dosage of Part II organic phosphorus compound is 10-90
Weight %；It is preferred that the dosage of Part I organic phosphorus compound is 30-40 weight %, the dosage of Part II organic phosphorus compound
For 60-70 weight %.
5. preparation method according to claim 1 or 2, wherein, the bar that the hydrolysis material is mixed with organic phosphorus compound
Part includes：Temperature is 60-100 DEG C, and/or the time is 1-10h；Preferable temperature is 70-90 DEG C, and/or the time is 2-4h.
6. preparation method according to claim 1 or 2, wherein, group VIII metal is cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium
It is preferably cobalt with the one or more in platinum.
7. preparation method according to claim 1 or 2, wherein, by silicon source, group VIII source metal and structure directing agent into
Row hydrolysis carries out in the presence of silylating reagent and/or the hydrolysis material is blended in silylating reagent with organic phosphorus compound
In the presence of carry out；It is preferred that the silicon source and the molar ratio of silylating reagent are SiO2：Silylating reagent=1：(0.001-0.1),
Preferably SiO2：Silylating reagent=1：(0.01-0.06)；It is preferred that the silylating reagent is the compound of below formula (I)：
R in formula (I)1、R2、R3And R4Halogen, alkyl, alkoxy, aromatic radical or amido are each independently, and at least one is
Alkyl, alkoxy, aromatic radical or amido；Preferably, the silylating reagent for dimethyldichlorosilane, methyl trichlorosilane,
The pungent methyl tetrasiloxane of trim,ethylchlorosilane, 1,7- dichloros, [3- trimethoxy silicon propyl group] dimethyloctadecylammonium ammonium bromide, N- benzene
Base -3- TSL 8330s, phenyl triethoxysilane, hexamethyldisilazane, hexamethyldisiloxane, methyl
In triethoxysilane, tert-butyl chloro-silicane, hexadecyl trimethoxy silane and octyltri-ethoxysilane extremely
Few one kind；More preferably phenyl triethoxysilane, three ethoxy of hexamethyldisilazane, hexamethyldisiloxane and methyl
At least one of base silane.
8. preparation method according to claim 7, wherein, this method includes：
(1) silicon source, group VIII source metal, Part I organic phosphorus compound and structure directing agent are hydrolyzed and are hydrolyzed
Material；
(2) crystallization is carried out after mixing hydrolysis material, Part II organic phosphorus compound and the silylating reagent；
It is preferred that being counted by 100 weight % of total dosage of the organic phosphorus compound, the dosage of Part I organic phosphorus compound is
10-90 weight %, the dosage of Part II organic phosphorus compound are 10-90 weight %, and the silicon source and silylating reagent rub
Your ratio is SiO2：Silylating reagent=1：(0.001-0.1)；It is preferred that the dosage of Part I organic phosphorus compound is 30-40 weights
Measure %, the dosage of Part II organic phosphorus compound is 60-70 weight %, and the molar ratio of the silicon source and silylating reagent is
SiO2：Silylating reagent=1：(0.01-0.06).
9. according to the preparation method described in any one in claim 1-8, wherein,
The organic phosphorus compound is the one or more in such as following formula (II), formula (III) and formula (IV),
Wherein, the R in formula (II), formula (III) and formula (IV) is respectively the one or more in alkyl, aryl and amido；It is preferred that
Ground
R in formula (II), formula (III) and formula (IV) is respectively the straight chained alkyl of C1-C18, the branched alkyl of C3-C18, C6-C16
Aryl and amido in one or more；More preferably
The organic phosphorus compound for triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, three iso-butyl ester of phosphoric acid, tricresyl phosphate oneself
One or more in ester, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate and tricresyl phosphate (2- chloropropyls) ester；
The silicon source be selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate, silica gel, white carbon and
At least one of Ludox；
The structure directing agent is selected from least one of fatty amines, alcamines and quaternary ammonium alkaloid compound, is preferably
Selected from least one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide；
Group VIII source metal is water miscible group VIII metallic compound, preferably described water miscible group VIII metal
Compound is cobalt trifluoride, six cyano cobalt acid potassium, hexanitro cobalt acid sodium, acetylacetone cobalt, six amino cobalt chlorides, three (2,4- penta
Two ketone acids) cobalt, the one or more in two (pentamethylcyclopentadiene base) hexafluorophosphoric acid cobalts；
The mol ratio that the condition of hydrolysis includes material is SiO2：Structure directing agent：Group VIII metal：H2O=1：
(0.001-5)：(0.0001-0.1)：(5-400), temperature are 10-120 DEG C, time 1-24h；
The condition of crystallization includes：Crystallization in confined conditions, temperature be 110-230 DEG C, and/or the time for 1-240 it is small when.
10. the siliceous molecular sieve that the preparation method in claim 1-9 described in any one is prepared.
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| CN114524720A (en) * | 2022-03-04 | 2022-05-24 | 江西师范大学 | Method for preparing phenylpropyl aldehyde by 1-phenethyl alcohol through dehydration-hydroformylation cascade reaction one-pot method |
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