CN102295534B - Method for preparing alpha, alpha-dimethyl benzyl alcohol - Google Patents
Method for preparing alpha, alpha-dimethyl benzyl alcohol Download PDFInfo
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- CN102295534B CN102295534B CN201010208155.6A CN201010208155A CN102295534B CN 102295534 B CN102295534 B CN 102295534B CN 201010208155 A CN201010208155 A CN 201010208155A CN 102295534 B CN102295534 B CN 102295534B
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Abstract
The invention relates to a method for preparing alpha, alpha-dimethyl benzyl alcohol, and mainly solves the problems that a large amount of sulfur-containing waste water is produced, heavy pollution is caused, the quality of a product is low, the energy consumption is high, production efficiency is low, and labor intensity is high in the prior art. The problems are solved by the technical scheme that olefin and dimethylbenzyl hydroperoxide which are used as raw materials and a catalyst are subjected to contact reaction in a fixed bead reactor at the temperature of between 0 and 150 DEG C and under the pressure of 0.1 to 10.0 MPa by taking a nonpolar organic compound which is inert to the reaction system as a solvent under the condition that the molar ratio of the olefin to the dimethylbenzyl hydroperoxide is 0.1-20:1, the weight ratio of dimethylbenzyl hydroperoxide to solvent is 0.01-9:1 and the weight space velocity of dimethylbenzyl hydroperoxide is 0.01 to 50 hours<-1> to form the alpha, alpha-dimethyl benzyl alcohol, wherein the catalyst is at least one of Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or amorphous Ti/SiO2, and the titanium in the catalyst is 0.1 to 20 percent of the weight of the catalyst. The method can be used for industrial production of alpha, alpha-dimethyl benzyl alcohol.
Description
Technical field
The present invention relates to a kind of α of preparation, the method for alpha-alpha-dimethyl benzylalcohol.
Background technology
α, alpha-alpha-dimethyl benzylalcohol is the important source material of preparing dicumyl peroxide (DCP).DCP is considered to industrial monosodium glutamate, and it,, as linking agent, can make polymkeric substance have three-dimensional structure, greatly improves physical property; For poly polymerization, its product can be used as the exterior of cable; For EVA cross-linked foam, can produce the foam materials with fine pores; For being cross-linked of EPM, EPDM, can improve insulativity, processibility and the thermotolerance of product.Also be the excellent vulcanizing agent of natural rubber, synthetic rubber and polyvinyl resin.
Current industrialized α, alpha-alpha-dimethyl benzylalcohol is at 60～65 ℃, uses Na
2sO
3or Na
2the S aqueous solution is prepared by reductive agent reduction hydrogen phosphide cumene (CHP).This technique produces a large amount of waste water, and 1 ton of DCP of every production will produce the sulfur-containing waste water of 2.5 tons of reduction, and COD, up to 3.4 ten thousand mg/L, also will produce a large amount of unpleasant poisonous hydrogen sulfide in last handling process.Along with the pay attention to day by day of country to " energy-saving and emission-reduction " work, the shortcoming of this technique is more obvious.And in order to ensure that hydrogen phosphide cumene is fully reduced, the consumption of sodium sulphite often will surpass theoretical consumption, the α producing like this, the alpha-alpha-dimethyl benzylalcohol product thing that usually can cure pollutes, thereby follow-up use procedure is had a negative impact.Shortcoming such as so prior art is deposited and produced aborning a large amount of sulfur-containing waste waters, seriously polluted, poor product quality, energy consumption is high, production efficiency is low, labour intensity is large.
Titaniferous porous silica material has good catalytic activity to the selective oxidation of hydro carbons, can be used as the catalyzer that epoxide is prepared in alkene selective oxidation.
Document US3923843 and US 4367342 disclose that to take the amorphous silica of titaniferous be catalyzer, and hydrogen peroxide ethylbenzene (EBHP) can be propylene oxide by-product α-methylbenzylalcohol by Selective Oxidation of Propylene.This patent just reacts hydrogen peroxide ethylbenzene and propylene to produce propylene oxide, and the α-methylbenzylalcohol of by-product for vinylbenzene, does not mention that take hydrogen phosphide cumene reacts as oxygenant and propylene or other alkene through further Dehydration.
Document CN1500004A and CN 1248579A disclose that to take hydrogen phosphide cumene (CHP) or hydrogen peroxide ethylbenzene (EBHP) be oxygenant, prepare the technology of propylene oxide with a kind of titanium-containing catalyst catalytic oxidation propylene of preparation process complexity.But this patent does not relate to α, the preparation technology of alpha-alpha-dimethyl benzylalcohol and other alkene react to prepare α, the process of alpha-alpha-dimethyl benzylalcohol with hydrogen phosphide cumene.
Summary of the invention
Technical problem to be solved by this invention is in prior art, exist to produce a large amount of sulfur-containing waste waters, seriously polluted, poor product quality, energy consumption is high, production efficiency is low, labour intensity is large problem, provides a kind of new preparation α, the method for alpha-alpha-dimethyl benzylalcohol.It is good that the method has selectivity, and reaction conditions is gentle, pollution-free, the feature that good product quality and production cost are low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of α for preparing, the method of alpha-alpha-dimethyl benzylalcohol, take alkene and hydrogen phosphide cumene as raw material, the nonpolar organic compound that reaction system is to inertia of take is solvent, in temperature of reaction, it is 0～150 ℃, reaction pressure is 0.1～10.0MPa, the mol ratio of alkene and hydrogen phosphide cumene is 0.1～20: 1, the weight ratio of hydrogen phosphide cumene and solvent is 0.01～9: 1, and the weight space velocity of hydrogen phosphide cumene is 001～50 hour
-1under condition, in fixed-bed reactor, reaction raw materials and catalyzer contact reacts obtain described α, alpha-alpha-dimethyl benzylalcohol; Wherein, described catalyzer is selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or unformed Ti/SiO
2in at least one; Wherein in catalyzer, titanium content is catalyst weight 01～20%.
In technique scheme, described catalyzer preferred version is for being selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 or unformed Ti/SiO
2in at least one, more preferably scheme is for being selected from Ti-HMS, Ti-MCM-41 or unformed Ti/SiO
2in at least one.In catalyzer, titanium content preferable range is catalyst weight 0.2～10%, and more preferably scope is 0.5～5%.Before catalyzer is used, preferably, with being dissolved in the organic silicon solution in organic solvent or using organosilicon steam treatment under gas phase condition, silanization temperature preferable range is 0～400 ℃, and more preferably scope is 50～350 ℃; Silanization treatment time preferable range is 0.5～48 hour, and more preferably scope is 1～24 hour.Organosilicon preferred version is at least one being selected from halosilanes, silazane or silylamine; Wherein said halosilanes preferred version is at least one being selected from trimethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, chlorodimethyl silane, dimethyldichlorosilane(DMCS), 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane, and more preferably scheme is for being selected from trimethylchlorosilane; Described silazane preferred version is for being selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-bis-(chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1, at least one in 3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1, at least one in 1,3,3-tetramethyl-disilazane; Described silylamine is selected from least one in N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.Organosilicon consumption is preferably 0.1～100% of catalyst weight, and more preferably scope is 1～50%.
In technique scheme, described alkene preferred version is for being selected from alkene, cycloolefin, aromatic olefin, chloro-alkenes or hydroxyl alkene; Wherein said alkene preferred version is for being selected from ethene, propylene, butylene, amylene or hexene; Described cycloolefin preferred version is for being selected from cyclopentenes, tetrahydrobenzene, cyclooctene or cyclododecene; Described aromatic olefin preferred version is for being selected from vinylbenzene or alpha-methyl styrene; Described chloro-alkenes preferred version is for being selected from propenyl chloride; Hydroxyl alkene preferred version is for being selected from vinyl carbinol.The described non-polar organic solvent preferred version that reaction system is to inertia is at least one being selected from benzene,toluene,xylene, ethylbenzene, diethylbenzene, isopropyl benzene, diisopropylbenzene(DIPB), normal butane, Trimethylmethane, pentane, normal hexane, hexanaphthene, heptane, octane, nonane, decane, undecane hydrocarbon or dodecane hydrocarbon, and more preferably scheme is for being selected from isopropyl benzene.Reaction conditions preferable range is: 40～130 ℃ of temperature of reaction, reaction pressure 0.1～6.0MPa, the mol ratio 05～15: 1 of alkene and hydrogen phosphide cumene, the weight ratio 0.1～4: 1 of hydrogen phosphide cumene and solvent, the weight space velocity of hydrogen phosphide cumene 0.1～20 hour
-1.
The catalyzer adopting in the present invention is titaniferous porous silica catalyzer, can be selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1 or unformed Ti/SiO
2in at least one, wherein in catalyzer, titanium content is catalyst weight 0.1～20%.This titaniferous porous silica catalyzer is by direct synthetic or rear grafting, to carry titanium to synthesize, there is meso-hole structure feature, as Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1, or there is macroporous structure feature, as unformed Ti/SiO
2.This titaniferous porous silica catalyzer is at 960 ± 10cm of infrared absorpting light spectra
-1all have charateristic avsorption band with the 210 ± 10nm place at uv-visible absorption spectra figure, this indicates that titanium has been grafted in silicon dioxide skeleton and has formed the active titanium species with four-coordination structure.
The present invention can prepare α according to hydrogen phosphide cumene through reductive agent reduction, the reaction mechanism of alpha-alpha-dimethyl benzylalcohol, on the porous silica catalyzer of highly active titaniferous, make hydrogen phosphide cumene and alkene generation redox reaction, hydrogen phosphide cumene is reduced to α, alpha-alpha-dimethyl benzylalcohol, reaction conditions is gentle, and selectivity is good.Preferred catalyst of the present invention carries out silanization processing before use, and the hydroxyl that its surface is existed is converted into alkyl siloxy, strengthens hydrophobicity, reduces acid.The hydrophobic raising of catalyzer can reduce polarity oxidation products in the absorption of catalyst surface, also can avoid the loss of active constituent titanium on catalyzer.Adopt the inventive method, than using Na
2sO
3or Na
2s does that reductive agent selectivity is the highest improves approximately 15%.The present invention adopts alkene rather than adopts Na
2sO
3or Na
2s makes reductive agent, so do not have sulfur-containing waste water to produce, does not have problem of environmental pollution, does not need to process waste water, and production cost is low.In addition, because adopted catalyzer is a kind of typical heterogeneous catalyst, so at the α that adopts the method to produce, in alpha-alpha-dimethyl benzylalcohol reaction solution, not containing catalyzer, product is not subject to catalyst contamination, good product quality; Compare with slurry bed reactor, fixed-bed reactor are easy to operate, and flow process is simple, do not need the unit operations such as catalyzer filtration, easily realize serialization scale operation, obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Under the mild stirring of chamber, 15.0g cetylamine is joined and contains 80ml H
2in the mixing solutions of O, 60ml ethanol and 5ml (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 4.0g tetrabutyl titanate that is dissolved in the 65.0g tetraethoxy in 30ml ethanol and be dissolved in 10ml ethanol is joined in above-mentioned mixing solutions simultaneously to crystallization 24h after stirring 30min.Then filter gained decorating film, wash with water.Material after washing, after 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is obtained to Ti-HMS catalyst Precursors.
In the there-necked flask of a 100ml, add the 50ml cumene solution that contains 4.0g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent, make the Ti-HMS catalyzer finished product of processing through silanization.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical HMS constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.2%.
[embodiment 2]
Method by [embodiment 1] makes Ti-HMS catalyst Precursors, and it is carried out to silanization processing, and just silylating reagent is trimethylchlorosilane.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical HMS constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.1%.
[embodiment 3]
Method by [embodiment 1] makes Ti-HMS catalyst Precursors, just it is not carried out to silanization processing.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical HMS constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.3%.
[embodiment 4]
Under the mild stirring of chamber, 15.0g cetylamine is joined and contains 80ml H
2in the mixing solutions of O, 60ml ethanol and 5ml (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 65.0g tetraethoxy being dissolved in 30ml ethanol is joined in above-mentioned mixing solutions to crystallization 24h after stirring 30min.Then filter gained decorating film, wash with water.Material after washing, after 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, must be had to the support of the catalyst of HMS constitutional features.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
450ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the TiCl of evaporated in vacuo remnants
4with isopropyl benzene solvent.After being cooled to 90 ℃, add distilled water 30ml and stir 10min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-HMS catalyst Precursors.
In the there-necked flask of a 100ml, add the 50ml cumene solution that contains 3.5g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent, make the Ti-HMS catalyzer of processing through silanization.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical HMS constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.4%.
[embodiment 5]
Method by [embodiment 4] makes Ti-HMS catalyst Precursors, and it is carried out to silanization processing, and just silylating reagent is dimethyldichlorosilane(DMCS).XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical HMS constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.5%.
[embodiment 6]
15.0g aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 24.0g 25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 60.0ml aqueous solution that contains 23.0g cetyl trimethylammonium bromide and forms clear solution subsequently.Above-mentioned mixing solutions be moved into in the stainless steel autoclave of polytetrafluoro liner in 100 ℃ of static crystallization 3 days.Product after crystallization, after washing, filtering, is dried 24h in 100 ℃, and 550 ℃ of roasting 6h must have the support of the catalyst of MCM-41 constitutional features.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
450ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the TiCl of evaporated in vacuo remnants
4with isopropyl benzene solvent.After being cooled to 90 ℃, add distilled water 30ml and stir 10min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-MCM-41 catalyst Precursors.
Method by [embodiment 4] is carried out silanization processing to the Ti-MCM-41 catalyst Precursors making, and makes final Ti-MCM-41 catalyzer finished product.XRD, N
2absorption, FT-IR and UV-Vis characterize and analytical results shows, this material has typical MCM-41 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.0%.
[embodiment 7]
Method by [embodiment 6] makes Ti-MCM-41 catalyst Precursors, and it is carried out to silanization processing, and just silylating reagent is dimethyldichlorosilane(DMCS).XRD, N
2absorption, FT-IR and UV-Vis characterize and analytical results shows, this material has typical MCM-41 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 29%.
[embodiment 8]
15.0g aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 24.0g 25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 60.0ml aqueous solution that contains 23.0g cetyl trimethylammonium bromide and forms clear solution subsequently.Under rapid stirring, 2.4g tetrabutyl titanate be slowly added drop-wise in above-mentioned mixing solutions and continue to stir 30min.Above-mentioned siliceous and mixing solutions titanium be moved into in the stainless steel autoclave of polytetrafluoro liner in 100 ℃ of static crystallization 3 days, make Ti-MCM-41 catalyst Precursors.
Method by [embodiment 4] is carried out silanization processing to the Ti-MCM-41 catalyst Precursors making, and makes final Ti-MCM-41 catalyzer finished product.XRD, N
2absorption, FT-IR and UV-Vis characterize and analytical results shows, this material has typical MCM-41 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.9%.
[embodiment 9]
Method by [embodiment 8] makes Ti-MCM-41 catalyst Precursors, just it is not carried out to silanization processing.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical MCM-41 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.1%.
[embodiment 10]
624g tetraethoxy and 2.04g tetrabutyl titanate are joined in 20ml dehydrated alcohol and form mixing solutions, under agitation 47.5g trolamine and 20ml distilled water are successively added drop-wise in above-mentioned mixing solutions, and 2.0h is stirred in continuation, then 35.5g tetraethyl ammonium hydroxide (25% the aqueous solution) is added drop-wise in above-mentioned solution and continues to stir 1h and form colourless transparent solution, aging 24h at room temperature subsequently, after 100 ℃ of aging 24h, in 700 ℃ of roasting 12h, obtain Ti-TUD-1 catalyst Precursors.
Method by [embodiment 4] is carried out silanization processing to the Ti-TUD-1 catalyst Precursors making, and makes final Ti-TUD-1 catalyzer finished product.XRD, N
2absorption, FT-IR and UV-Vis characterize and analytical results shows, this material has typical TUD-1 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.3%.
[embodiment 11]
Method by [embodiment 10] makes Ti-TUD-1 catalyst Precursors, just adopts N-trimethyl-silyl-imidazole, as silylating reagent, it is carried out to silanization processing.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical TUD-1 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.4%.
[embodiment 12]
At 40 ℃, 24.0g segmented copolymer (P123) is dissolved in the hydrochloric acid soln that 1L concentration is 2mol/L, under agitation 68.0g tetraethoxy joined in above-mentioned solution and continue to stir 24h, then transferred to in the stainless steel cauldron of polytetrafluoro liner in 100 ℃ of crystallization 48h.After product after crystallization is filtered, washs, is dried, in 550 ℃ of roasting 6h, obtain support of the catalyst SBA-15.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
450ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the TiCl of evaporated in vacuo remnants
4with isopropyl benzene solvent.After being cooled to 90 ℃, add distilled water 30ml and stir 10min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-SBA-15 catalyst Precursors.
Method by [embodiment 4] is carried out silanization processing to the Ti-SBA-15 catalyst Precursors making, and makes final Ti-SBA-15 catalyzer finished product.XRD, N
2absorption, FT-IR and UV-Vis characterize and results of elemental analyses shows, this material has typical SBA-15 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.4%.
[embodiment 13]
Method by [embodiment 12] makes Ti-SBA-15 catalyst Precursors, just adopts aminomethyl phenyl chlorosilane, as silylating reagent, it is carried out to silanization processing.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical SBA-15 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.1%.
[embodiment 14]
By tetraethoxy, cetyl trimethylammonium bromide, EDTA and H
2o 1: 0.25: 1 in molar ratio: 60 ratio mix and stir after be transferred in the stainless steel cauldron with polytetrafluoro liner, at 100 ℃ of constant temperature 24h, re-adjustments pH value is in 10.5 left and right, after constant temperature secondary, product is taken out, and to be washed with distilled water to pH value be 7.0 left and right, after oven dry prior in nitrogen atmosphere 550 ℃ of roastings 1 hour, more roasting 6h obtains KIT-1 support of the catalyst in air atmosphere.In the there-necked flask of a 100ml, add and contain 4.0gTiCl
450ml cumene solution, the support of the catalyst 20.0g of above-mentioned preparation is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the TiCl of evaporated in vacuo remnants
4with isopropyl benzene solvent.After being cooled to 90 ℃, add distilled water 30ml and stir 10min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-KIT-1 catalyst Precursors.
Method by [embodiment 4] is carried out silanization processing to the Ti-KIT-1 catalyst Precursors making, and makes final Ti-KIT-1 catalyzer finished product.XRD, N
2absorption, FT-IR and UV-Vis characterize and results of elemental analyses shows, this material has typical KIT-1 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 2.8%.
[embodiment 15]
Method by [embodiment 14] makes Ti-KIT-1 catalyst Precursors, just adopts aminomethyl phenyl chlorosilane, as silylating reagent, it is carried out to silanization processing.XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical KIT-1 constitutional features and Ti has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.1%.
[embodiment 16]
Under the mild stirring of chamber, 4.3g tetrabutyl titanate is joined to the ethanolic soln that forms tetrabutyl titanate in 20ml ethanol, the commercially available silica gel that 20.0g drying treatment is crossed (80-120 order, specific surface area 340m
2/ g, pore volume 0.71cm
3/ g, mean pore size
) join in 60ml ethanol.Then under nitrogen atmosphere, the ethanolic soln of tetrabutyl titanate is added drop-wise in the ethanolic soln that contains commercially available silica gel, filters after at room temperature stirring this mixture 2h, by washing with alcohol filtrate three times.In air atmosphere, in 110 ℃ of solid 12h of drying after above-mentioned filtration, at 600 ℃ of roasting 4h, obtain the unformed Ti/SiO of catalyst Precursors.
In the there-necked flask of 100 milliliters, add the 50ml cumene solution that contains 4.0g hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in flask, under stirring and refluxing, rising temperature to 150 ℃, and react 4h at this temperature.Then at this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent, make the unformed Ti/SiO processing through silanization
2catalyzer finished product.FT-IR and UV-Vis characterize and results of elemental analyses shows, titanium has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.0%.
[embodiment 17]
The commercially available silica gel that 20.0g drying was processed (80-120 order, specific surface area 340m
2/ g, pore volume 071cm
3/ g, mean pore size
) be immersed in 60ml octane solvent.Under stirring and nitrogen atmosphere, will be dissolved with 2.4g TiCl
420ml octane mixture be added drop-wise in above-mentioned paste mixture, be warming up to 100 ℃ after constant temperature stirring and refluxing 2h, temperature to 150 ℃ solvent evaporated then raises under vacuum condition.
The sample of above-mentioned acquisition is put in quartz tube reactor, in nitrogen atmosphere, rising temperature to 700 ℃, and at this roasting temperature 2h, reduce the temperature to after 300 ℃ nitrogen purging 2h.Further reduce temperature to 220 ℃, at this temperature, the nitrogen that contains 60g trimethylchlorosilane saturation steam is passed through to beds, then use nitrogen purging 2h, make the unformed Ti/SiO processing through silanization
2catalyzer finished product.FT-IR and UV-Vis characterize and results of elemental analyses shows, titanium has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.2%.
[embodiment 18]
Method by [embodiment 17] makes unformed Ti/SiO
2catalyst Precursors, does not just carry out silanization processing to it.FT-IR, UV-Vis characterize and results of elemental analyses shows, titanium has entered skeleton, has formed the active titanium of four-coordination, and wherein the weight content of titanium is 1.3%.
[embodiment 19～36]
Propylene catalytic reduction hydrogen phosphide cumene is prepared α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 4.0g of [embodiment 1～18] (being crushed to 20～40 orders after compression molding) is loaded in the stainless steel fixed-bed reactor that internal diameter is 10mm, raw material 30 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is solvent) and propylene adopt respectively two volume pumps to squeeze into reactor, the flow of CHP solution is 0.85g/min, the flow of propylene is 0.56g/min, system pressure is 3.0MPa, temperature of reaction is 90 ℃, average response result between employing reaction times 48～96h is as catalyst performance evaluation result, and reaction result is in Table 1.
Table 1
[embodiment 37～54]
Tetrahydrobenzene catalytic reduction hydrogen phosphide cumene is prepared α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 4.0g of [embodiment 1～18] (being crushed to 20～40 orders after compression molding) is loaded in the stainless steel fixed-bed reactor that internal diameter is 10mm, raw material 30 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is solvent) and tetrahydrobenzene adopt respectively two volume pumps to squeeze into reactor, the stream flow of CHP solution is 0.45g/min, the flow of tetrahydrobenzene is 0.15g/min, system pressure is 0.5MPa, temperature of reaction is 85 ℃, average response result between employing reaction times 48～96h is as catalyst performance evaluation result, and reaction result is in Table 2.
Table 2
[embodiment 55～72]
Cyclooctene catalytic reduction hydrogen phosphide cumene is prepared α, alpha-alpha-dimethyl benzylalcohol (DMBA)
The catalyzer 4.0g of [embodiment 1～18] (being crushed to 20～40 orders after compression molding) is loaded in the stainless steel fixed-bed reactor that internal diameter is 10mm, raw material 30 (weight) % hydrogen phosphide cumene (CHP, isopropyl benzene is solvent) and cyclooctene adopt respectively two volume pumps to squeeze into reactor, the stream flow of CHP solution is 0.45g/min, the flow of cyclooctene is 0.20g/min, system pressure is 0.5MPa, temperature of reaction is 85 ℃, the average response result that employing reaction times 48～96h asks is as catalyst performance evaluation result, and reaction result is in Table 3.
Table 3
[comparative example 1]
Take the hydrogen phosphide cumene solution (CHP of 608g 50 (weight) %, isopropyl benzene is solvent) join in three mouthfuls of glass flask of 200ml with reflux condensing tube, during rising temperature to 65 ℃, start magnetic agitation, slowly by the Na of 14.5g 30 (weight) %
2the S aqueous solution is added drop-wise in flask, treats Na
2after the S aqueous solution dropwises, continue stirring reaction 30min, can think that reaction finishes.Take out reaction product and analyze, draw by analysis the α of generation, the weight of alpha-alpha-dimethyl benzylalcohol (DMBA) is 20.6g, produces containing 7.5gNa simultaneously
2sO
4and Na
2the about 18.0g of waste water of S.The transformation efficiency of hydrogen phosphide cumene and α, the selectivity of alpha-alpha-dimethyl benzylalcohol (DMBA) is in Table 4.
[comparative example 2]
The hydrogen phosphide cumene solution (CHP, solvent is isopropyl benzene) that takes 60.8g 50 (weight) % joins in three mouthfuls of glass flask of 200ml with reflux condensing tube, during rising temperature to 65 ℃, starts magnetic agitation, slowly by the Na of 104g25%
2sO
3the aqueous solution is added drop-wise in flask, treats Na
2sO
3after the aqueous solution dropwises, continue stirring reaction 30min, can think that reaction finishes.Take out oil phase reaction product and carry out chromatogram and iodometric titrationiodimetry titration analysis, draw by analysis the α of generation, the weight of alpha-alpha-dimethyl benzylalcohol (DMBA) is 20.2g, produces containing 29.3g containing Na simultaneously
2sO
4and Na
2sO
3waste water 108.0g.The transformation efficiency of hydrogen phosphide cumene and α, the selectivity of alpha-alpha-dimethyl benzylalcohol (DMBA) is in Table 4.
Table 4
Claims (1)
1. prepare a α, the method for alpha-alpha-dimethyl benzylalcohol, step is as follows:
(1) preparation of catalyst Precursors
At 40 ℃, 24.0g segmented copolymer P123 is dissolved in the hydrochloric acid soln that 1L concentration is 2mol/L, under agitation 68.0g tetraethoxy joined in above-mentioned solution and continue to stir 24h, then transferred to in the stainless steel cauldron of polytetrafluoro liner in 100 ℃ of crystallization 48h; After product after crystallization is filtered, washs, is dried, in 550 ℃ of roasting 6h, obtain support of the catalyst SBA-15; In the there-necked flask of a 100ml, add and contain 4.0gTiCl
450ml cumene solution, the support of the catalyst of above-mentioned preparation is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature, then at this temperature, the TiCl of evaporated in vacuo remnants
4with isopropyl benzene solvent; After being cooled to 90 ℃, add distilled water 30ml and stir 10min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-SBA-15 catalyst Precursors;
(2) preparation of catalyzer
In the there-necked flask of a 100ml, add the 50ml cumene solution that contains 3.5g aminomethyl phenyl chlorosilane, the catalyst Precursors of the above-mentioned preparation of 10.0g is joined in flask, at rapid stirring with under refluxing, rising temperature to 150 ℃, and react 4h at this temperature; Then at this temperature, the aminomethyl phenyl chlorosilane of evaporated in vacuo remnants and isopropyl benzene solvent, make the Ti-SBA-15 catalyzer of processing through silanization; XRD, N
2absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows, this material has typical SBA-15 constitutional features, and Ti entered skeleton, have formed the active titanium of four-coordination, and wherein the weight content of titanium is 3.1%;
(3) propylene catalytic reduction hydrogen phosphide cumene is prepared α, alpha-alpha-dimethyl benzylalcohol
Above-mentioned Ti-SBA-15 catalyzer is crushed to 20～40 orders after compression molding, taking 4.0g is loaded in the stainless steel fixed-bed reactor that internal diameter is 10mm, concentration is that cumene solution and the propylene of 30 (weight) % hydrogen phosphide cumene adopts respectively two volume pumps to squeeze into reactor, the flow of hydrogen phosphide cumene solution is 0.85g/min, the flow of propylene is 0.56g/min, system pressure is 3.0MPa, temperature of reaction is 90 ℃, adopt the average response result between reaction times 48～96h to be: the transformation efficiency of hydrogen phosphide cumene is 97.2%, α for hydrogen phosphide cumene, the selectivity of alpha-alpha-dimethyl benzylalcohol is 96.7%.
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