CN101115561B - Method for manufacturing titanium-containing silicon oxide catalyst, catalyst and method for manufacturing alkylene oxide using the catalyst - Google Patents
Method for manufacturing titanium-containing silicon oxide catalyst, catalyst and method for manufacturing alkylene oxide using the catalyst Download PDFInfo
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Abstract
A process for producing a titanium-containing silicon oxide catalyst which comprises the following steps (A) and (B); and a catalyst obtained by the process. Step (A): a step in which a silica source part or all of which is a silicon compound having a silicon atom having a hydrocarbon group directly bonded thereto is mixed by stirring with a titanium source and a molding-agent solution to obtain a solid containing the catalyst ingredient and the molding agent, the proportion of water in the solvent in the molding-agent solution being 50 wt.% or lower or a step in which a silica source which comprises a combination of an organic silicon source comprising a silicon compound having a silicon atom having a hydrocarbon group directly bonded thereto with a silicon compound having no carbon-silicon bonds is mixed by stirring with a titanium source and a molding-agent solution to obtain a solid containing the catalyst ingredient and the molding agent, the addition of the silica source to the molding-agent solution being conducted so as to satisfy the relationship: (amount of the organic silica source added in the first half)>(amount of the organic silica source added in the latter half). Step B: a step in which the molding agent is removed from the solid obtained in the step (A).
Description
Technical field
The present invention relates to manufacturing approach, this catalyst of silicon oxide catalyst containing titanium and the manufacturing approach of using the olefinated oxygen compound of this catalyst.
Background technology
In the presence of catalyst, the method that is obtained olefinated oxygen compound by hydroperoxides and olefin type compound is known.As use therein catalyst, can enumerate the titaniferous silicide catalyst, in order to obtain high performance catalyst, carried out improving hydrophobic trial.
For example; Open flat 10-72212 communique the spy, the spy opens 2002-320860 communique, Chem.Commun., (1998) 1899, Chem.Lett., (2001) 648, Stud.Surf.Sci.Catal.; 141 (2002) 189 and J.Mater.Chem.; In 12 (2002) 3078, disclose specific silicon oxide catalyst containing titanium, this catalyst improves hydrophobicity through using the silicon compound of alkyl Direct Bonding on silicon atom as the catalyst raw material., from realize higher activity and optionally viewpoint see that these catalyst still are difficult to the catalyst of saying so and can fully satisfy.
Summary of the invention
The object of the present invention is to provide the manufacturing approach of silicon oxide catalyst containing titanium and the catalyst that obtains through this manufacturing approach; It can be used for for example being obtained by hydroperoxides and olefin type compound the reaction of olefinated oxygen compound, and can bring into play high activity and high selectivity.
That is, the present invention provides a kind of manufacturing approach of silicon oxide catalyst containing titanium, and it satisfies the condition of following (1)～(3), and comprises following operation A and B.
(1) average pore size is more than
;
(2) aperture that has
more than 90% of total hole volume; And
(3) specific pore volume is long-pending is 0.2cm
3More than/the g.
Operation A:
(I) use part or all of alkyl Direct Bonding the silicon compound on the silicon atom (below; Be called the organosilicon source) as the silicon source; With this silicon source and titanium source and template solution mixing stirring; Thereby obtain containing the operation of the solid of catalyst component and template, wherein, the ratio of the water in the solvent of template solution is below the 50 weight %; Perhaps
(II) use comprise the organosilicon source of the silicon compound of alkyl Direct Bonding on silicon atom and comprise do not have carbon-the inorganic silicon source of the silicon compound of silicon key is as the silicon source; With this silicon source and titanium source and template solution mixing stirring; Thereby obtain containing the operation of the solid of catalyst component and template; Wherein, the relational expression below in the process of in template solution, adding the silicon source, satisfying:
Amount in the organosilicon source of preceding half section interpolation>amount (so-called preceding half section be meant begin during half molal quantity that adds silicon source total amount (mole)) in the organosilicon source of adding in the second half section from adding the silicon source, and
Process B: the operation of from the solid that operation A obtains, removing template.
The present invention also provides a kind of silicon oxide catalyst containing titanium, and it is to obtain through above-mentioned manufacturing approach.
In addition, the present invention also provides a kind of manufacturing approach of olefinated oxygen compound, wherein, in the presence of the silicon oxide catalyst containing titanium that obtains through above-mentioned manufacturing approach, makes the reaction of olefin type compound and hydroperoxides.
The specific embodiment
The catalyst that the present invention obtains is the catalyst that comprises the titanium-containing silicon oxide of the condition that satisfies following (1)～(3).
Condition (1) is that average pore size is more than
;
Condition (2) is the aperture that has
more than 90% of total hole volume;
Condition (3) is the long-pending 0.2cm of being of specific pore volume
3More than/the g.Here, the long-pending pore volume that is meant every 1g catalyst of so-called specific pore volume.
For the mensuration of above-mentioned condition (1)～(3), can use the physisorphtion of gases such as nitrogen, argon, carry out according to usual way.Can there be the peak that shows interplanar crystal spacing d in the catalyst that obtains among the present invention in X-ray diffraction (XRD), also can not exist.Here the peak of said demonstration interplanar crystal spacing d is to come from the crystallinity that solid has and the peak of regularity, also can have the wide peak that comes from pars amorpha.
See from highly active viewpoint, this catalyst preferably in infrared absorption spectroscopy at 960 ± 5cm
-1The zone have absworption peak.Can think that this peak is corresponding to importing to the intraskeletal titanium of silica.
Satisfying the catalyst of above-mentioned condition (1)～(3) makes through the manufacturing approach with following operation A and B.
As operation A, adopt following operation:
(I) use the silicon compound of part or all of alkyl Direct Bonding on silicon atom as the silicon source; And with this silicon source and titanium source and template solution mixing stirring; Thereby obtain containing the operation of the solid of catalyst component and template; Wherein, the ratio of the water in the solvent of template solution is below the 50 weight %; Perhaps
(II) use comprise the organosilicon source of the silicon compound of alkyl Direct Bonding on silicon atom and comprise do not have carbon-the inorganic silicon source of the silicon compound of silicon key is as the silicon source; And with this silicon source and titanium source and template solution mixing stirring; Thereby obtain containing the operation of the solid of catalyst component and template; Wherein, when in template solution, adding the silicon source, the relational expression below satisfying:
Amount in the organosilicon source of preceding half section interpolation>amount in the organosilicon source of adding in the second half section
(so-called preceding half section be meant begin during half molal quantity that adds silicon source total amount (mole)) from adding the silicon source.
In (I) of operation A, when silicon source, titanium source and template solution being mixed stirring, the ratio of using the water in this solvent is the solvent of the following solvent of 50 weight % as template.The above-mentioned raw materials that uses can dissolve or be dispersed in the solvent and use during as solid, shaped.
Mixed method is not special to be limited, but preferably adds silicon source and titanium source in the solution of template method usually.
In addition, in (II) of operation A, when in template solution, adding the silicon source, the relational expression below importantly satisfying.
Amount in the organosilicon source of preceding half section interpolation>amount in the organosilicon source of adding in the second half section
(so-called preceding half section be meant begin during half molal quantity that adds silicon source total amount (mole)) from adding the silicon source.
Wherein, preceding half section of the interpolation in the silicon source of the total amount in preferred organosilicon source is added in the template solution.If satisfy above-mentioned relation, then can organosilicon source and inorganic silicon source be mixed, add again after being adjusted into the concentration of expectation, also can their not mixed but progressively add, can also make up these methods, not special the qualification.
In operation A (II), has following characteristic:, can cut down the amount in necessary organosilicon source, thereby can obtain high performance catalyst at an easy rate in order to obtain high-activity high-selectivity catalyst.
As the example of the silicon compound of alkyl Direct Bonding on silicon atom in the organosilicon source of using as raw material among the present invention, can enumerate monoalkyltrialkoxysi.ane, dialkyl dialkoxy silicane, trialkyl-single alkoxy silane, two (trialkoxysilyl) alkane, single aryl trialkoxy silane, diaryl dialkoxy silicane, two (trialkoxysilyl) aromatic hydrocarbons etc.These can use separately, also can mix multiple use.Wherein, Preferred monoalkyltrialkoxysi.ane and/or the single aryl trialkoxy silane of using; For example; As alkyl or aryl, can enumerate the alkyl of carbon numbers 1～16 such as methyl, ethyl, propyl group, butyl, vinyl, acrylic, cyclopentenyl, cyclohexenyl group, phenyl, tolyl, xylyl, naphthyl.In addition, abovementioned alkyl, aryl can also have the substituting group that comprises N, O, P, halogen etc.As alkoxyl, can enumerate the alkoxyl of carbon numbers 1～6 such as methoxyl group, ethyoxyl, propoxyl group, butoxy.As the object lesson in organosilicon source, can enumerate trimethoxymethylsila,e, trimethoxy-benzene base silane, dimethoxy dimethylsilane, triethoxy methyl silicane, triethoxyphenylsilan, diethoxy diethylsilane, tripropoxy methyl-monosilane, three butoxymethyl silane etc.
In order to strengthen the silica skeleton in the catalyst; The silicon compound (inorganic silicon source) that can amorphous silica or alkoxy silane etc. not had carbon-silicon key; For example original quanmethyl silicate, tetraethyl orthosilicate, orthosilicic acid orthocarbonate etc. preferably mix use with above-mentioned organosilicon source with using in above-mentioned organosilicon source.
In operation A (I); When using the mixture in organosilicon source and inorganic silicon source; The ratio of mixing is not special to be limited; But preferably mix 5 moles more than the %, more preferably 5～50 moles of %, further the organosilicon source of preferred 10～30 moles of % (total amount in organosilicon source and inorganic silicon source is made as 100 moles of %).
In addition, also not special qualification the in operation A (II), the use amount in organosilicon source is preferably 5～50 moles of %, more preferably the scope of 10～30 moles of % (total amount in organosilicon source and inorganic silicon source is made as 100 moles of %).
As the titanium source; Can enumerate alkoxytitanium; For example; Metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate, butyl titanate, metatitanic acid four isobutyl esters, metatitanic acid four (2-Octyl Nitrite), metatitanic acid four (stearyl) or hydroxyl acetyl acetone titanium (IV), diisopropoxy bis-acetylacetonate are closed titanium (IV) etc., perhaps halogenated titanium, for example titanium tetrachloride, titanium tetrabromide, titanium tetra iodide etc. or titanyl sulfate etc.
As template, can use cationic surfactants such as alkylammonium, dialkyl ammonium, trialkyl ammonium, hexadecyldimethyl benzyl ammonium, alkyl pyridine; Anion surfactants such as alkylsurfuric acid salt ion, alkyl phosphoric acid salt ion; In the non-ionic surface active agents such as polyalkylene oxide or their block copolymer, alkylamine any one.Wherein, preferably use the quaternary ammonium ion of formula (I) expression:
[NR
1R
2R
3R
4]
+ (I)
(in the formula, R
1The straight chain shape of expression carbon number 2～36 or the alkyl of branched, R
2～R
4The alkyl of expression carbon number 1～6) or alkyl pyridine ion.
R
1Be the straight chain shape of carbon number 2～36 or the alkyl of branched, preferred carbon number is 10～18.R
2～R
4Be the alkyl of carbon number 1～6, preferred R
2～R
4Be methyl.Object lesson as the quaternary ammonium ion of general formula (I) expression; Can enumerate cations such as cetyltrimethyl ammonium, dodecyl trimethyl ammonium, benzyltrimethylammon.um, dimethyl two (dodecyl) ammonium; As the alkyl pyridine ion, can enumerate cations such as cetyl pyridinium.
In addition, these compounds that are used for template can use separately, also can mix multiple use.
As the example of the solvent that makes template dissolving, can enumerate water or alcohol, for example methyl alcohol, ethanol, normal propyl alcohol, 2-propyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, vinyl alcohol, allyl alcohol, cyclohexanol, benzylalcohol etc. or dihydroxylic alcohols, perhaps their mixture etc.
In above-mentioned operation A (I), importantly making the ratio of the water in the solvent of template dissolving is below the 50 weight %, is preferably 5～40 weight %, more preferably 10～30 weight %.Thus, can obtain to realize the catalyst of high activity and high selectivity.
Then, operation A (II) is described.
Use silicon compound (organosilicon source) and the inorganic silicon source that do not have carbon-silicon key of alkyl Direct Bonding on silicon atom as the silicon source; And this silicon source and titanium source and template mixed stirring in solvent; Thereby obtain containing the solid of catalyst component and template; But when in template solution, adding the silicon source, the relational expression below satisfying:
Amount in the organosilicon source of preceding half section interpolation>amount in the organosilicon source of adding in the second half section
(so-called preceding half section be meant begin during half molal quantity that adds silicon source total amount (mole)) from adding the silicon source.
As stated, through adopting the adding method in silicon source in template solution, that can make high activity, high selectivity contains the Ti catalyst.
Above-mentioned compound can be used in organosilicon source, the inorganic silicon source of in the method for operation A (II), using, and for compound, the template in titanium source, also can use above-mentioned compound.In addition, in operation A (II),, can use the above-mentioned solvent of enumerating as the solvent of template, but unqualified for the content of water, can be not moisture yet.But, as the solvent of the template among the operation A (II), the preferred solvent that uses the condition that satisfies operation A (I).
Below, describe in more detail, short of special instruction, then and (II) applicable to operation A (I).
The titanium source is 10 with respect to the use amount in silicon source with molar ratio computing
-5～1, be preferably 0.00008～0.4.Quaternary ammonium ion is preferably 10 with respect to the use amount of the total amount in these silicon sources and titanium source with molar ratio computing
-2～2.
In addition, in order to promote the reaction in silicon source and titanium source, preferably give alkalescence or acidity to mixed solution.As alkali source, preferred quaternary ammonium hydroxide, as an example; Can enumerate TMAH, tetraethyl ammonium hydroxide, TPAOH etc.; Particularly during as template, there is no need to add alkali source, more preferably at the hydroxide of the quaternary ammonium ion that uses general formula (I) expression.As the example of acid, can enumerate organic acids such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and formic acid, acetate, propionic acid.
Mix the temperature that stirs and be generally-30～100 ℃.Though generate solid through mixing to stir, in order to make the solid further growth, can be with its slaking.Curing time was generally below 180 hours, and curing temperature is generally 0～200 ℃.When slaking need be heated,, preferably transfer to airtight carrying out in the pressure vessel for fear of the gasification of solvent.
Process B is the operation of from solid, removing template.
Removing of template can realize that wherein preferred the extraction removed through the solid enforcement solvent extraction operation or the baking operation that contain catalyst component and template that operation A is obtained.
Whitehurst etc. have reported the technology (with reference to No. 5143879 communiques of United States Patent (USP)) that adopts the solvent extraction template.The solvent that uses during extraction be so long as can dissolve the solvent of the compound that template uses and get final product, and that can use carbon number from 1 to about 12 usually is liquid oxa-and/or oxo replacement hydrocarbon at normal temperatures.As preferred this kind solvent, can use alcohols, ketone, ethers (non-annularity and ring-type) and ester class, for example can enumerate hydroxyls such as methyl alcohol, ethanol, ethylene glycol, propane diols, isopropyl alcohol, n-butanol and octanol and replace hydrocarbon; Oxos such as acetone, metacetone, MEK and methyl iso-butyl ketone (MIBK) replace hydrocarbon; Hydrocarbyl ethers such as diisobutyl ether or oxolane; And the ester of hydrocarbon such as methyl acetate, ethyl acetate, butyl acetate and butyl propionate etc., but see preferred alcohols, wherein more preferably methyl alcohol from the viewpoint of the solvability of template.These extract solvent and do not limit with respect to the weight ratio of the solid that contains catalyst component and template is special, but are generally 1～1000, are preferably 5～300.In order to improve extraction effect, can in these solvents, add acid or their salt.As the example of the acid of using, can enumerate organic acids such as inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid and formic acid, acetate, propionic acid.As their example of salt, can enumerate alkali metal salt, alkali salt, ammonium salt etc.Acid of adding or their concentration of salt in solvent are preferably below the 10mol/l, more preferably below the 5mol/l.If acid of adding or their concentration of salt in solvent are excessive, the titanium stripping that then exists in the catalyst component, catalytic activity reduces sometimes.
With after extracting solvent and fully mixing, through filtering or method separation liquid phase part such as decant with the solid that contains catalyst component and template.Necessary number of times is carried out in this operation repeatedly.Can also extract template through following method: the solid that will contain catalyst component and template is filled in the pipe etc., and makes and extract solvent and circulate.The completion of solvent extraction can be confirmed through for example analyzing liquid phase part.Extract temperature and be preferably 0～200 ℃, more preferably 20～100 ℃.When the boiling point of extraction solvent is low, can also pressurizes and extract.
Extract to handle that template in the solution that the back obtains can reclaim and utilize again as the template raw material of operation A.In addition, likewise, extract solvent and can adopt common purifying such as distillation procedure and utilization again.
The extraction solvent that contains in the solid after extracting operation can be removed through drying process, when then carrying out silanization, and can also be with the inactive in fact solvent exchange of the silanizing agent that uses in the silanization operation is removed.
Under the situation that drying is removed,, can enumerate taper drying machine or board-like drying machine that warm braw or decompressor have been installed as drying device.
Under the situation that displacement is removed, use the inactive in fact solvent of the silanizing agent that uses in the silanization operation of following is replaced the extraction solvent that contains in the solid.The replacement solvent that displacement is used in the operation is so long as nonactive in fact to silanizing agent, and satisfies this condition of extraction dissolution with solvents of using in the process B is got final product.
The solvent that in the displacement operation, preferably uses is generally carbon number 1 and under about 12 normal temperature, is liquid hydro carbons, halogenated hydrocarbon, ketone, ethers, ester class, N; N-disubstituted amide class, nitrile, tertiary amines for example can be enumerated hexane, cyclohexane, chloroform, benzene,toluene,xylene, acetone, metacetone, MEK, methyl iso-butyl ketone (MIBK), ether, diisobutyl ether, oxolane 、 diox, methyl acetate, ethyl acetate, dimethyl formamide, acetonitrile, pyridine, triethylamine, methyl-sulfoxide etc.From seeing with the relation of the silanization operation of following, preferred replacement solvent is a hydro carbons, wherein more preferably toluene.These solvents both can use separately, also can use and mix multiple solution.
In replacement operator, with obtain in replacement solvent and the process B contain the solid that extracts solvent and fully mix after, through filtering or method such as decant is separated liquid phase part.This operation is repeated necessary number of times.In addition, can also be filled in the reaction tube etc., the method for replacement solvent circulation is replaced through containing the solid that extracts solvent.See from the productive viewpoint of catalyst, preferably from process B of the present invention to after the silanization operation stated all same reactor, carry out.The completion of this replacement operator can be confirmed through for example analyzing liquid phase part.The displacement temperature is preferably 0～200 ℃, more preferably 20～100 ℃.When the boiling point of the solvent that uses in this operation is low, can also pressurizes and replace.
In addition, the replacement solvent of using in the displacement operation can be removed the extraction solvent through usual ways such as distillation or extractions, and utilizes again.
The solid that passes through operation A of the present invention and process B and obtain has high hydrophobicity; And can be used as high-activity high-selectivity catalyst and work; But handle through above-mentioned solid further being implemented silanization, can obtain the catalyst of the silanization that performance further is enhanced.
Silanization can carry out with vapor phase method, and the solid reaction that in this vapor phase method gasiform silanizing agent and process B is obtained also can carry out with liquid phase method, in solvent, makes silanizing agent and solid reaction in this liquid phase method, and the present invention is liquid phase method more preferably.In general, when adopting liquid phase method to carry out silanization, preferably use hydro carbons.Removing through replacement operator when extracting solvent,, seeing from the viewpoint of utilizing again of solvent, preferably identical solvent though that the silanization solvent there is no need is certain identical with replacement solvent.
The example of silanizing agent can be enumerated organosilan, Organosilyl amine, Organosilyl acid amides and derivative thereof and organosilazanes and other silanizing agent.
As the example of organosilan, can enumerate trim,ethylchlorosilane, dimethyldichlorosilane, dimethyl chloride bromo-silicane, nitrotrimethylolmethane methyl-monosilane, chlorotriethyl silane, dimethylbutyl iodine silane, 3,5-dimethylphenyl chlorosilane, dimethylchlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, tert-butyl chloro-silicane, tripropyl chlorosilane, dimethyl octyl group chlorosilane, tributyl chlorosilane, three hexyl chloride silane, dimethyl ethyl chlorosilane, dimethyl stearyl chlorosilane, normal-butyl dimethylchlorosilane, bromomethyl dimethylchlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, 3-chloropropyl dimethylchlorosilane, dimethoxy-methyl chlorosilane, aminomethyl phenyl chlorosilane, triethoxy chlorosilane, 3,5-dimethylphenyl chlorosilane, methyl phenyl vinyl chlorosilane, benzyl dimethyl chlorosilane, diphenyl chlorosilane, diphenyl methyl chloro silane, diphenylacetylene chlorosilane, tribenzyl chlorosilane, 3-cyanic acid propyl-dimethyl chlorosilane.
As the example of Organosilyl amine, can enumerate N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silicyl imidazoles, N-dimethyl isopropyl silicyl imidazoles, N-trimethyl silyl amine, N-trimethyl silyl dimethylamine, N-trimethyl silyl diethylamine, N-trimethyl silyl pyrroles, N-trimethyl silyl pyrrolidines, N-trimethyl silyl piperidines, 1-amino-ethyl (diethylamino) dimethylsilane, pentafluorophenyl group dimetylsilyl amine.
Example as Organosilyl acid amides and derivative thereof; Can enumerate N; The two trimethyl silyl acetamides of O-, N; The two trimethyl silyl trifluoroacetamides of O-, N-trimethyl silyl acetamide, N-methyl-N-trimethyl silyl acetamide, N-methyl-N-trimethyl silyl trifluoroacetamide, N-methyl-N-trimethyl silyl five fluorine butyramides, N-(t-butyldimethylsilyl)-N-TFA amine, N, two (the diethyl hydrogen silicyl) trifluoroacetamides of O-.
As the example of organosilazanes, can enumerate HMDS, heptamethyldisilazane, 1,1,3; 3-tetramethyl-disilazane, 1, two (chloromethyl) tetramethyl-disilazanes, 1 of 3-, 3-divinyl-1,1; 3,3-tetramethyl-disilazane, 1,3-diphenyl tetramethyl-disilazane.
As other silanizing agent; Can enumerate N-methoxyl group-N; The two trimethyl silyl trifluoroacetamides of O-, N-methoxyl group-N; The two trimethyl silyl carbamates of O-, N, the two trimethyl silyl sulfamates of O-, trimethylsilyl triflate, N, N '-two trimethyl silyl ureas.
Preferred silanizing agent is a HMDS.
The catalyst of the present invention operation of the solid forming through will containing catalyst component usually is processed into molded catalyst bodies.Moulding can be after above-mentioned template be removed the front and back, solvent exchange operation of operation and any stage after the silanization operation carry out; But see from the viewpoint of the deterioration of catalyst rerum naturas such as rejection ratio surface area or pore volume, preferably before template is removed operation, carry out.Forming method can use arbitrary method such as compression forming, extrusion molding.In extrusion molding, can use normally used organic and inorganic bond, but add the reduction that adhesive can cause catalyst activity sometimes.When the manufacturing of this molded catalyst bodies, see most preferably compression forming method from the viewpoint of catalyst strength and catalyst rerum natura.
As the compression forming method, can enumerate roll-forming (briquetting, compacting), oil pressure moulding, compression molding etc.The pressure of compression is generally 0.1～10 ton/cm
2, be preferably 0.2～5 ton/cm
2, 0.5～2 ton/cm more preferably
2If hypotony, then the intensity of formed body is insufficient sometimes, and on the other hand, if hypertonia, then the hole is destroyed, and the catalyst rerum natura is insufficient sometimes.When carrying out compression forming, the solid that contains catalyst component preferably contains the moisture of appropriate amount, thus, even adopt low compression pressure also can make the formed body of abundant intensity.The moisture content that is used for the material of compression forming is preferably 1～70 weight %, more preferably 5～40 weight %.Amount of moisture can the aridity when making wet solid drying be regulated, and also can in the solid of abundant drying, add entry and regulate.In addition, not bringing in the scope of obstacle, can also add normally used adhesive etc. to the performance of expectation.
The shape of molded catalyst bodies can be a shape arbitrarily such as tablet, ball, ring.Can directly be used for reaction etc. with this shape, also can be ground into suitable size back and use.
Therefore catalyst, except being used for selective oxidation reaction, for example beyond the epoxidation Reaction of Alkenes, can also be used for each kinds of oxidation reaction of organic compound owing to have the titanium active site of high surface area and high degree of dispersion and high hydrophobicity.In addition, as required, can also be used for alkylated reaction or catalytic reforming reaction etc. through adding the acid sites of three one-tenth powerful catalysts of assigning to further add of aluminium oxide grade in an imperial examination.
Particularly, catalyst of the present invention can be applicable to the manufacturing approach of the olefinated oxygen compound that makes olefin type compound and hydroperoxides reaction.
The olefin type compound can be non-ring type, monocyclic, dicyclic or polycyclic compound, also can be the compound of monoolefine type, alkadienes type or polyene type.When having 2 above alkene keys, it can be that conjugated bonds also can be non-conjugated bonds.The olefin type compound that usually preferred carbon number is 2～60.Can also have substituting group, but the preferred more stable group of substituting group.The example of such hydrocarbon can be enumerated ethene, propylene, butene-1, isobutene, hexene-1, hexene-2, hexene-3, octene-1, decylene-1, styrene, cyclohexene etc.The example of preferred alkadienes type compound can be enumerated butadiene, isoprene.Can also have substituting group, its example can be enumerated halogen atom, in addition, can also existence contains the various substituting groups of aerobic, sulphur, nitrogen-atoms simultaneously with hydrogen and/or carbon atom.Preferred especially olefin type compound is an olefin type unsaturated alcohol and with the substituted olefin type unsaturated hydrocarbons of halogen atom, and its example can be enumerated allyl alcohol, crotonyl alcohol, allyl chloride.Particularly preferably be carbon number and be 3～40 alkene, this alkene can also be replaced by hydroxyl or halogen atom.
As the example of hydroperoxides, can enumerate organic hydroperoxide.Organic hydroperoxide is to have general formula:
R-O-O-H
The compound of (wherein, R is the alkyl of 1 valency), this compound and the reaction of olefin type compound generate olefinated oxygen compound and compound R-OH.Preferred group R is the group with 3～20 carbon atoms.Most preferably radicals R is alkyl, the particularly second month in a season or the tertiary alkyl or the aralkyl of 3～10 of carbon numbers.In these groups; Preferred especially group is tertiary alkyl, and the second month in a season or uncle's aralkyl; Its object lesson can be enumerated the tert-butyl group, tertiary pentyl, cyclopenta, 2-phenyl propyl-2 base, in addition, also can enumerate from the aliphatic lateral chain of tetrahydronaphthalene molecule and remove hydrogen atom and the various tetrahydro naphthyls that generate.
When using cumene hydroperoxide as organic hydroperoxide, the hydroxy compounds that the result obtains is 2-phenyl-2-propyl alcohol.This material can be transformed into AMS through dehydration.AMS is useful material in industry.
When using t-amyl hydroperoxide as organic hydroperoxide, the uncle's amylene that is produced by the dehydration of the tert-pentyl alcohol that obtains is the useful material as the isoprene precursor.Tert-pentyl alcohol also is useful as the precursor of the tert amyl methyl ether(TAME) of octane enhancer.When using tert-butyl hydroperoxide as organic hydroperoxide, the tert-butyl alcohol that obtains is the useful material as the precursor of the methyl tertiary butyl ether(MTBE) of octane enhancer.
As the example of the hydroperoxides beyond the organic hydroperoxide, can enumerate hydrogen peroxide.
Hydrogen peroxide is that chemical formula is the compound of HOOH, can obtain with the form of the aqueous solution usually.Hydrogen peroxide and the reaction of olefin type compound generate alkylene oxide compound and water.
The organic hydroperoxide and the hydrogen peroxide that use as raw material can be rare or dense purifying thing or non-purifying things.
Epoxidation reaction can use solvent and/or diluent in liquid phase, to implement.Solvent and diluent must be to be liquid under the temperature and pressure when reaction, and reactant and product are come down to inactive material.Solvent can also be included in the material that exists in the employed hydrogen peroxide solution.For example, cumene hydroperoxide is when comprising the mixture of cumene hydroperoxide and raw material isopropylbenzene thereof, need not add solvent especially, can use it to replace solvent.
The temperature of epoxidation reaction is generally 0～200 ℃, preferred 25～200 ℃ temperature.Pressure can be to make reactant mixture keep the sufficient pressure of liquid condition.Usually, pressure is that 100～10000kPa is favourable.
After epoxidation reaction finished, the liquefied mixture that contains the product of expectation can easily separate from carbon monoxide-olefin polymeric.Then, can adopt appropriate method with the liquefied mixture purifying.Purifying comprises fractionation, slective extraction, filtration, washing etc.Solvent, catalyst, unreacted alkene type compound, unreacted hydroperoxides can also recycle and utilize again.
Of the present inventionly used the reaction of catalyst to carry out, under the situation of large-scale industrial operation, preferably used fixed bed with the form of slurry, fixed bed.This reaction can adopt batch process, semi-continuous process or continuity method to implement.The liquid that contains reagent the liquefied mixture that comes out from conversion zone, does not contain catalyst fully or does not contain catalyst in fact during through fixed bed.
Embodiment
Below, through embodiment the present invention is described.
Embodiment 1
The preparation of catalyst fines
To stir by the cetyltrimethylammonium hydroxide of 16 weight %, the methyl alcohol of 64 weight %, the template solution 125.0g (water in the solvent is 20/ (64+20)=24 weight %) that the water of 20 weight % constitutes, and under 50 ℃ to the mixed solution of the 2-propyl alcohol that wherein drip to add 1.85g tetraisopropyl titanate and 10.0g.Stir after 30 minutes, drip the mixed solution of 30.5g original quanmethyl silicate and 6.8g MTMS.Then, continue down to stir 3 hours at 50 ℃.The deposition that filtration obtains producing.
Be deposited in 70 ℃ of following drying under reduced pressure 8 hours with what obtain.
The making of formed body
Dry to 30.0g and in the white solid that obtains spraying add the water of 4.5g, and with abundant mixed mixture with the compression forming of tablet former.The solid that obtains is pulverized, used sieve to obtain the molded catalyst bodies of 1.0～2.0mm then.1.0mm compression forming is carried out in following solid circulation utilization once more.
The extraction of template is removed
Then, the above-mentioned formed body that obtains of 11.5g is filled in the glass post of internal diameter 16mm φ, with LHSV=6h
-1In post, feed following liquid successively with up flow type: under (1) room temperature, under the methyl alcohol of 100ml, (2) the 45 ℃ of heating, under the mixed solution of the methyl alcohol of 200ml and 4g concentrated hydrochloric acid (content 36 weight %), (3) the 45 ℃ of heating, the methyl alcohol of 200ml.After liquid feed to finish, extract the methyl alcohol in the post out from the bottom of post, under 80 ℃ of heating, with 10mmHg with molded catalyst bodies drying under reduced pressure 1.5 hours.
Synthesizing of propylene oxide (PO)
Use 25% cumene hydroperoxide (CHPO) and propylene (C
3') estimate the above-mentioned molded catalyst bodies that obtains by batch reaction device (autoclave).With the CHPO of 1.0g catalyst, 30.0g, the C of 16.6g
3' join in the autoclave, under self-generated pressure, react under 1.5 hours time in 85 ℃ of reaction temperatures, reaction (comprising intensification).Reaction result is as shown in table 1.
Embodiment 2
Silanization
The molded catalyst bodies that 3.0g embodiment 1 obtains is put in the glass flask that cooling tube has been installed, added 2.0g HMDS and 30.0g toluene, under 110 ℃ of heating, carry out 1.5 hours silanizations.After the fluid separation applications, under 110 ℃ of heating with 10mmHg with molded catalyst bodies drying under reduced pressure 1.5 hours.Average pore size through using the molded catalyst bodies that obtains that nitrogen measures as the physisorphtion of gas is 29 dusts, and the ratio of pore volume in total hole volume with aperture of 5～200 dusts is 94%, and specific pore volume is long-pending is 0.87ml/g.
According to adopting the batch reaction device that the silylation catalyst that obtains is estimated with embodiment 1 same method.Reaction result is as shown in table 1.
Comparative example 1
Except the template solution 125.0g (water in the solvent is 73/ (11+73)=87 weight %) that the water that uses by the methyl alcohol of the cetyltrimethylammonium hydroxide of 16 weight %, 11 weight %, 73 weight % constitutes; Likewise prepare molded catalyst bodies with embodiment 1; Estimate with the batch reaction device, reaction result is as shown in table 1.
Comparative example 2
With embodiment 2 likewise, the molded catalyst bodies that comparative example 1 is obtained carries out silanization, estimates with the batch reaction device, reaction result is as shown in table 1.
Embodiment 3
The preparation of catalyst fines
To stir by the cetyltrimethylammonium hydroxide of 16 weight %, the methyl alcohol of 66 weight %, the template solution 125.0g (water in the solvent is 18/ (66+18)=21 weight %) that the water of 18 weight % constitutes, under 50 ℃ to the mixed solution of the 2-propyl alcohol that wherein drip to add 1.85g tetraisopropyl titanate and 10.0g.Stir after 30 minutes, drip the mixed solution (preceding half section) of 15.2g (100mmol) original quanmethyl silicate and 3.4g (25mmol) MTMS.Add 19.1g (125mmol) original quanmethyl silicate (second half section) afterwards, continue to stir 3 hours down at 50 ℃.Filter the deposition that produces.
Be deposited in 70 ℃ of following drying under reduced pressure 8 hours with what obtain.
The making of formed body
Dry to 25.0g and in the white solid that obtains spraying add the water of 3.8g, and with abundant mixed mixture with the compression forming of tablet former.The solid that obtains is pulverized, used sieve to obtain the molded catalyst bodies of 1.0～2.0mm then.1.0mm compression forming is carried out in following solid circulation utilization once more.
The extraction of template is removed
Then, the above-mentioned formed body that obtains of 11.5g is filled in the glass post of internal diameter 16mm φ, with LHSV=6h
-1In post, feed following liquid successively with up flow type: under (1) room temperature, under the methyl alcohol of 100ml, (2) the 45 ℃ of heating, under the mixed solution of the methyl alcohol of 200ml and 4g concentrated hydrochloric acid (content 36 weight %), (3) the 45 ℃ of heating, the methyl alcohol of 200ml.After liquid feed to finish, extract the methyl alcohol in the post out from the bottom of post, under 80 ℃ of heating, with 10mmHg with molded catalyst bodies drying under reduced pressure 1.5 hours.
Synthesizing of propylene oxide (PO)
Except using the above-mentioned molded catalyst bodies that obtains, likewise carry out the synthetic of PO with embodiment 1.Reaction result is as shown in table 1.
Embodiment 4
When adding the silicon source; Behind preceding half section adding 19.1g (125mmol) original quanmethyl silicate; Drip the mixed solution of 15.2g (100mmol) original quanmethyl silicate and 3.4g (25mmol) MTMS in the second half section; In addition, likewise prepare molded catalyst bodies, estimate with the batch reaction device with embodiment 3.Reaction result is as shown in table 1.
Embodiment 5
When adding the silicon source; All drip the mixed solution of 30.4g (200mmol) original quanmethyl silicate and 6.8g (50mmol) MTMS at preceding half section, second half section; In addition, likewise prepare molded catalyst bodies, estimate with the batch reaction device with embodiment 3.Reaction result is as shown in table 1.
Industrial applicability
According to the present invention; The manufacturing approach of silicon oxide catalyst containing titanium and the catalyst that obtains through this manufacturing approach can be provided; It can be used for for example obtaining the reaction of olefinated oxygen compound from hydroperoxides and olefin type compound, and can bring into play high activity and high selectivity.
Claims (7)
1. the manufacturing approach of silicon oxide catalyst containing titanium, this catalyst satisfies the condition of following (1)～(3), and this manufacturing approach comprises following operation A and B,
(1) average pore size is more than
;
(2) total hole volume has an aperture of 5～
more than 90%; And
(3) specific pore volume is long-pending is 0.2cm
3More than/the g, operation A:
(I) use the silicon compound of part or all of alkyl Direct Bonding on silicon atom as the silicon source; With this silicon source and titanium source and template solution mixing stirring; Thereby obtain containing the operation of the solid of catalyst component and template; Wherein, the ratio of the water in the solvent of template solution is below the 50 weight %, and
Process B: the operation of from the solid that operation A obtains, removing template.
2. the described method of claim 1, wherein, the template of in operation A, using is the quaternary ammonium ion of formula (a) expression,
[NR
1R
2R
3R
4]
+ (a)
In the formula, R
1The straight chain shape of expression carbon number 2～36 or the alkyl of branched, R
2～R
4The alkyl of expression carbon number 1～6.
3. claim 1 or 2 described methods, wherein, the silicon compound of alkyl Direct Bonding on silicon atom that uses among the operation A is monoalkyltrialkoxysi.ane and/or single aryl trialkoxy silane.
4. claim 1 or 2 described methods, wherein, the template of process B is removed through the solvent extraction operation and is carried out.
5. claim 1 or 2 described methods wherein, are carried out silanization and are handled removing solid after the template.
6. silicon oxide catalyst containing titanium, it obtains through each described method in the claim 1～5.
7. the manufacturing approach of olefinated oxygen compound wherein, in the presence of the described catalyst of claim 6, makes the reaction of olefin type compound and hydroperoxides.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004352358A JP2006159058A (en) | 2004-12-06 | 2004-12-06 | Method for manufacturing titanium-containing silicon oxide catalyst and catalyst |
| JP352357/2004 | 2004-12-06 | ||
| JP2004352357A JP4834982B2 (en) | 2004-12-06 | 2004-12-06 | Method for producing titanium-containing silicon oxide catalyst and catalyst |
| JP352358/2004 | 2004-12-06 | ||
| PCT/JP2005/022417 WO2006062111A1 (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin oxide compound with the catalyst |
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|---|---|---|---|
| CN2012100482679A Division CN102600820A (en) | 2004-12-06 | 2005-11-30 | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst |
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| ES2885530T3 (en) * | 2015-02-17 | 2021-12-14 | Lyondell Chemical Tech Lp | Method for preparing a catalyst |
| KR102493560B1 (en) * | 2017-04-07 | 2023-01-30 | 스미또모 가가꾸 가부시끼가이샤 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| KR20200131306A (en) | 2018-03-15 | 2020-11-23 | 스미또모 가가꾸 가부시키가이샤 | Method for producing a titanium-containing silicon oxide molded article, and a titanium-containing silicon oxide molded article |
| TWI698398B (en) * | 2019-03-22 | 2020-07-11 | 東聯化學股份有限公司 | Method and application of synthesizing titanium-containing silicon oxide material using biopolymer |
| WO2020241052A1 (en) * | 2019-05-29 | 2020-12-03 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide |
| CN111905707B (en) * | 2020-08-04 | 2023-05-12 | 长江大学 | Amorphous mesoporous TiO 2 -SiO 2 Catalyst and preparation method thereof |
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| CN1247101A (en) * | 1998-08-04 | 2000-03-15 | 住友化学工业株式会社 | Silicon oxide catalyst containing titanium |
| US6284696B1 (en) * | 1996-06-07 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Mesopore molecular sieve and process for the production thereof |
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| JP3577681B2 (en) * | 1995-08-29 | 2004-10-13 | 日本化学工業株式会社 | Method for producing mesoporous metallosilicate |
| JP4026884B2 (en) * | 1996-06-07 | 2007-12-26 | 旭化成株式会社 | Mesopore molecular sieve and method for producing the same |
| US6960671B2 (en) * | 2002-09-20 | 2005-11-01 | Arco Chemical Technology, L.P. | Process for direct oxidation of propylene to propylene oxide and large particle size titanium silicalite catalysts for use therein |
| JP4265212B2 (en) * | 2002-12-19 | 2009-05-20 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide catalyst |
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| US6284696B1 (en) * | 1996-06-07 | 2001-09-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Mesopore molecular sieve and process for the production thereof |
| CN1247101A (en) * | 1998-08-04 | 2000-03-15 | 住友化学工业株式会社 | Silicon oxide catalyst containing titanium |
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| JP4834982B2 (en) | 2011-12-14 |
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