CN102295625B - Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol - Google Patents
Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol Download PDFInfo
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Abstract
The invention relates to a method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol. The method mainly solves the problems of serious production process pollution, poor product quality and high production cost when the 1,2-epoxy cyclohexane and the alpha, alpha-dimethyl benzyl alcohol are separately produced in the prior art. Isopropyl benzene hydroperoxide and cyclohexene undergo oxidation-reduction reaction on a titanium-containing porous silicon dioxide catalyst under the mild reaction condition, wherein the isopropyl benzene hydroperoxide is reduced into the alpha, alpha-dimethyl benzyl alcohol, and the cyclohexene is oxidized into the 1,2-epoxy cyclohexane; and meanwhile, by adjusting the molar ratio of the cyclohexene to the isopropyl benzene hydroperoxide in the raw materials, the cyclohexene is totally converted or has little residue in the reaction process. According to the technical scheme, the problems are well solved, and the method can be used for industrial production of producing the 1,2-epoxy cyclohexane and the alpha, alpha-dimethyl benzyl alcohol.
Description
Technical field
The present invention relates to a kind of HEO and α, the co-production of alpha-alpha-dimethyl benzylalcohol.
Background technology
1,2-epoxy cyclohexane is a kind of important organic synthesis intermediate, because of the epoxy group(ing) on its molecular structure very active, can react with amine, phenol, alcohol, carboxylic acid etc., generate a series of derivatives, can be widely used in the fields such as medicine, agricultural chemicals, solidifying agent, softening agent, thinner, tensio-active agent.With the synthetic agricultural chemicals propargite of HEO, be that higher effective and lower toxic pesticide is welcome by peasant deeply.The hexanedial being synthesized by HEO is widely used in oil production and process hides.In addition, as epoxide resin reactive diluent, in economy and performance, more have superiority.
The major industry production method of HEO is two chlorohydrinations.This method produces a large amount of chlorine-contained wastewaters in process of production, and equipment corrosion and environmental pollution are serious; Need to use chlorine, this has problems raw material supply and safety simultaneously.In addition, can also from the waste liquid of cyclohexane oxidation hexalin processed and pimelinketone, extract and reclaim HEO.But because waste liquid quantity is limited, its scale is difficult to improve, and can not meet market demand.CN1880310 discloses a kind of employing quaternary ammonium salt phosphor-tungstic heteropoly acid and has made catalyzer, prepares the method for HEO with hydrogen peroxide oxidation tetrahydrobenzene.But because catalyst separating difficulty, turnover rate are higher, and the HEO cost that the reason such as catalyzer and hydrogen peroxide price height causes adopting this technology to produce is high.
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.
Industrial at present, 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.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.
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 carrys out cyclohexene oxide as oxygenant 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.
In sum, in prior art and unexposed coproduction HEO and α, the method of alpha-alpha-dimethyl benzylalcohol, and produce separately HEO and α, during alpha-alpha-dimethyl benzylalcohol, have that production technique is seriously polluted, poor product quality, problem that production cost is high.
Summary of the invention
Technical problem to be solved by this invention is that prior art is producing 1 separately, 2-epoxy cyclohexane and α, during alpha-alpha-dimethyl benzylalcohol, have that production technique is seriously polluted, poor product quality, problem that production cost is high, provide a kind of new 1,2-epoxy cyclohexane and α, the co-production of alpha-alpha-dimethyl benzylalcohol.The method can obtain HEO and α simultaneously, alpha-alpha-dimethyl benzylalcohol product, and it is high to have catalyst activity and 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 HEO and α, and the co-production of alpha-alpha-dimethyl benzylalcohol, comprises the following steps:
A) take tetrahydrobenzene 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 20～150 ℃, reaction pressure is 0.1～10.0MPa, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 0.1～1: 1, the weight percentage of hydrogen phosphide cumene in solvent is 1.0～90%, and the weight space velocity of hydrogen phosphide cumene is 0.01～20 hour
-1under condition, in reactor, reaction raw materials and catalyzer contact reacts obtain logistics I; Wherein said 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; In catalyzer, titanium content is catalyst weight 0.1～20%;
B) logistics I enters knockout tower, and after rectifying, tower top obtains logistics II, and tower reactor obtains logistics III;
C) logistics II enters hexanaphthene tower, and after rectifying separation, tower top obtains hexanaphthene, and tower reactor obtains logistics IV;
D) logistics IV enters HEO tower, and after rectifying separation, tower top obtains product HEO, and tower reactor obtains solvent;
E) logistics III enters hydrogenator, obtains logistics V after reaction;
F) logistics V enters α, alpha-alpha-dimethyl benzylalcohol tower, and after rectifying separation, tower top obtains product α, alpha-alpha-dimethyl benzylalcohol, tower reactor obtains solvent.
In technique scheme, a) described in step catalyzer preferred version 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, 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 0.3～1: 1 of tetrahydrobenzene and hydrogen phosphide cumene, the weight percentage of hydrogen phosphide cumene in solvent is 5～50%, and the weight space velocity of hydrogen phosphide cumene is 0.1～10 hour
-1.Described reactor preferred version is for being selected from fixed-bed reactor or paste state bed reactor.
The present invention, catalyzer a) adopting in step 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, the content of titanium is catalyst weight 0.1～20%.This titaniferous porous silica catalyzer is synthetic for carrying titanium by direct synthetic or rear grafting, has 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.
In the inventive method, knockout tower, hexanaphthene tower, HEO tower, α, alpha-alpha-dimethyl benzylalcohol tower and R-201 hydrogenator can be taked operational condition well known in the art.The preferred operations condition of knockout tower is: absolute pressure of top of the tower is 0.02～0.06MPa, and tower top temperature is 70～140 ℃, and tower reactor temperature is 120～160 ℃.The preferred operations condition of hexanaphthene tower is: absolute pressure of top of the tower is 0.03～0.1MPa, and tower top temperature is 60～90 ℃, and tower reactor temperature is 90～140 ℃.The preferred operations condition of HEO tower is: absolute pressure of top of the tower is 0.02～0.08MPa, and tower top temperature is 100～140 ℃, and tower reactor temperature is 120～160 ℃.α, the preferred operations condition of alpha-alpha-dimethyl benzylalcohol tower is: absolute pressure of top of the tower is 0.01～0.06MPa, and tower top temperature is 120～160 ℃, and tower reactor temperature is 150～210 ℃.The preferred operations condition of hydrogenator is: 50～90 ℃ of temperature of reaction, reaction pressure 0.5～1.5MPa, H
2the mol ratio of/hydrogen phosphide cumene (4～20): 1, air speed 0.3～5.0 hour
-1; Wherein hydrogenation catalyst used is for can be converted into hydrogen phosphide cumene shortening α, and the catalyzer of alpha-alpha-dimethyl benzylalcohol, can be selected from known Raney's nickel catalyst, Ni/AlO
3, Pd/C or Pd/AlO
3at least one in catalyzer.
The present invention can prepare α according to hydrogen phosphide cumene through reductive agent reduction, the reaction mechanism of alpha-alpha-dimethyl benzylalcohol, and organic hydroperoxide can catalyzed oxidation produce epoxides under catalyzer exists reaction characteristics, novelty combines two kinds, ground reaction mechanism.Under gentle reaction conditions, on the porous silica catalyzer of titaniferous, make hydrogen phosphide cumene and tetrahydrobenzene generation redox reaction, wherein hydrogen phosphide cumene is reduced to α, alpha-alpha-dimethyl benzylalcohol, tetrahydrobenzene is oxidized to 1 simultaneously, 2-epoxy cyclohexane, catalyst activity is high, good product selectivity.Like this, by a reaction, can produce the fine chemical product of two kinds of high added values, meet atom economy chemical principle.Preferred catalyst of the present invention before use, carries out silanization processing, 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.The present invention adopts alkene rather than Na
2sO
3, Na
2s is as reductive agent, and needs chlorine to make raw material unlike two chlorohydrinations are produced HEOs, so do not have sulfur-bearing, chlorine-contained wastewater and corresponding waste residue to produce, do not have problem of environmental pollution.Because adopted catalyzer is a kind of typical heterogeneous catalyst, so at the HEO and the α that adopt the method to produce, in alpha-alpha-dimethyl benzylalcohol reaction solution, not containing catalyzer, product purity is high, good product quality.
In addition,, in industrial tetrahydrobenzene raw material, because the boiling point of hexanaphthene and tetrahydrobenzene is very approaching, be difficult to obtain the tetrahydrobenzene product that purity is higher, so always contain relatively large hexanaphthene in tetrahydrobenzene product.Adopt such tetrahydrobenzene to make raw material through after its catalytic oxidation-reduction reaction and recycling, hexanaphthene amount in reaction product can accumulate gradually, for guaranteeing that tetrahydrobenzene needs as the purity of reaction raw materials, need carry out separation of extractive distillation purification to tetrahydrobenzene and hexanaphthene.The present invention is by regulating the mol ratio of raw material tetrahydrobenzene and hydrogen phosphide cumene, tetrahydrobenzene is completely converted in reaction process or residual volume seldom, the value not recycling, separated without again itself and remaining hexanaphthene being carried out, so can save the extracting rectifying unit of hexanaphthene and tetrahydrobenzene.
In the present invention, mol ratio≤1 due to raw material tetrahydrobenzene and hydrogen phosphide cumene, in reactor discharging, contain a certain amount of hydrogen phosphide cumene, therefore the present invention increases a hydrogenator, at the light constituent containing HEO, is distilled after separating, to containing isopropyl benzene, α at the bottom of tower, the heavy constituent of alpha-alpha-dimethyl benzylalcohol and hydrogen phosphide cumene is carried out hydrotreatment, by the hydrogen phosphide cumene hydrocracking that does not participate in reaction, is α, alpha-alpha-dimethyl benzylalcohol.So not only farthest improved product α, the yield of alpha-alpha-dimethyl benzylalcohol, has strengthened the economy of technology, has also further improved handiness and the security of production operation, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
In Fig. 1, R-101 is reactor, and T-201 is knockout tower, and T-202 is hexanaphthene tower, and T-203 is HEO tower, and T-204 is α, alpha-alpha-dimethyl benzylalcohol tower, and R-201 is hydrogenator, and 1 is hexanaphthene, and 2 is HEO, and 3 is solvent, 4 is H
2, 5 is α, alpha-alpha-dimethyl benzylalcohol, and 6 is tetrahydrobenzene, 7 is hydrogen phosphide cumene.
In Fig. 1, tetrahydrobenzene 6 and hydrogen phosphide cumene 7 carry out redox reaction under the existence of catalyzer and solvent in R-101, and reacted logistics I enters knockout tower T-201, and after rectifying, tower top obtains logistics II, and tower reactor obtains logistics III.Logistics II enters hexanaphthene tower T-202, and after rectifying separation, tower top obtains hexanaphthene 1, and tower reactor obtains logistics IV.Logistics IV enters HEO tower T-203, and after rectifying separation, tower top obtains product HEO 2, and tower reactor obtains solvent 3.Logistics III enters hydrogenator R-201, and remaining hydrogen phosphide cumene is carried out to hydrotreatment, logistics III and H
2after reaction, obtain logistics V.Logistics V enters α, alpha-alpha-dimethyl benzylalcohol tower T-204, and after rectifying separation, tower top obtains solvent 3, and tower reactor obtains product α, alpha-alpha-dimethyl benzylalcohol 5.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
30.0kg aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 48.0kg25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 120.0L aqueous solution that contains 46.0kg cetyl trimethylammonium bromide and forms clear solution subsequently.Above-mentioned mixing solutions is moved in crystallizing kettle, adds 0.1kgMCM-41 as crystal seed, 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 reactor, add and contain 8.0kgTiCl
4100L cumene solution, the support of the catalyst of above-mentioned preparation is joined in reactor, under stirring and 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 60L and stir 30min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-MCM-41 catalyst Precursors.
In another reactor, add the 100L cumene solution that contains 4.0kg hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 20.0kg is joined in reactor, 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 Ti-MCM-41 catalyzer of processing through silanization.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 3.8%.
[embodiment 2]
30.0kg aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 48.0kg25wt%, and continuously stirring 30min forms solution.Under agitation above-mentioned solution is joined in the 120.0L aqueous solution that contains 46.0kg cetyl trimethylammonium bromide and forms clear solution subsequently.Under rapid stirring, 4.8kg tetrabutyl titanate be slowly added drop-wise in above-mentioned mixing solutions and continue to stir 30min.The mixing solutions of above-mentioned siliceous and titanium is moved in crystallizing kettle, add 0.1kgTi-MCM-41 as crystal seed, in 100 ℃ of static crystallization 3 days, make Ti-MCM-41 catalyst Precursors.
Method by [embodiment 1] is carried out silanization processing to the Ti-MCM-41 catalyst Precursors making, and just silylating reagent adopts 1,1,3,3-tetramethyl-disilazane, and its consumption is 3.0kg, makes through the Ti-MCM-41 of silane treatment 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 2.1%.
[embodiment 3]
Method by [embodiment 1] makes Ti-MCM-41 catalyzer, just catalyzer is not carried out to silanization processing.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 4.5%.
[embodiment 4]
Under the mild stirring of chamber, 30.0kg cetylamine is joined and contains 160L H
2in the mixing solutions of O, 120L ethanol and 10L (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 8.0kg tetrabutyl titanate that is dissolved in the 130.0kg tetraethoxy in 60L ethanol and be dissolved in 20L 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.
Method by [embodiment 1] is carried out silanization processing to catalyzer, and just silylating reagent adopts trimethylchlorosilane, and its consumption is 8.0kg, makes 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 2.5%.
[embodiment 5]
Under the mild stirring of chamber, 30.0kg cetylamine is joined and contains 160L H
2in the mixing solutions of O, 120L ethanol and 10L (1mol/L) hydrochloric acid, be stirred to solution and be a phase.The 130.0kg tetraethoxy being dissolved in 60L 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 reactor, add and contain 8.0kgTiCl
4100L cumene solution, the support of the catalyst of above-mentioned preparation is joined in reactor, under stirring and 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 60L and stir 30min, the temperature to 110 that then raises ℃ evaporating water, makes Ti-HMS catalyst Precursors.
Method by [embodiment 1] is carried out silanization processing to catalyzer, and just the consumption of silylating reagent is 5.0kg, makes 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 2.8%.
[embodiment 6]
Method by [embodiment 4] makes Ti-HMS catalyzer, just catalyzer 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 2.7%.
[embodiment 7]
Under the mild stirring of chamber, 8.6kg tetrabutyl titanate is joined to the ethanolic soln that forms tetrabutyl titanate in 40L ethanol, the commercially available silica gel that 40.0kg drying treatment is crossed (80-120 order, specific surface area 340m
2/ g, pore volume 0.71cm
3/ g, mean pore size
) join in 120L ethanol.Then under nitrogen atmosphere, the ethanolic soln of tetrabutyl titanate is joined in the ethanolic soln that contains commercially available silica gel, filter 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 catalyst Precursors Ti/SiO
2.
Method by [embodiment 1] is carried out silanization processing to catalyzer, and just the consumption of silylating reagent is 2.0kg, makes the Ti/SiO processing through silanization
2catalyzer.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 1.2%.
[embodiment 8]
The commercially available silica gel that 40.0kg drying treatment is crossed (80-120 order, specific surface area 340m
2/ g, pore volume 0.71cm
3/ g, mean pore size
) be immersed in 120L octane solvent.Under stirring and nitrogen atmosphere, will be dissolved with 4.8kgTiCl
440L octane mixture join 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 ℃, pass into saturated steam and process 2h, nitrogen purging 2h.Make catalyst Precursors Ti/SiO
2.
Method by [embodiment 1] is carried out silanization processing to catalyzer, and just silylating reagent adopts trimethylchlorosilane, makes the Ti/SiO processing through silanization
2catalyzer.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 1.7%.
[embodiment 9]
Method by [embodiment 8] is prepared Ti/SiO
2catalyzer, 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 2.0%.
[embodiment 10～14]
By the method Kaolinite Preparation of Catalyst of [embodiment 1], [embodiment 3], [embodiment 5], [embodiment 8] and [embodiment 9], just support of the catalyst is before supported titanium respectively, and first extruded moulding, is processed into the preformed catalyst carrier of suitable fixed-bed reactor application.The titanium content of corresponding catalyst is respectively 3.6%, 4.3%, 2.7%, 1.8% and 1.9.
[embodiment 15]
By initial loadings, be that the Ti-MCM-41 catalyst loading prepared by [embodiment 1] of 20.0kg is in the stainless steel slurry reactor still R-101 with agitator, purity is that the tetrahydrobenzene (all the other are hexanaphthene) of 95.0wt% and the cumene solution of the hydrogen phosphide cumene that concentration is 30.0wt% are driven in reactor by volume pump respectively, obtains logistics I after reaction.The temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 80 ℃, and reaction pressure is 0.5MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 0.95, and the weight space velocity of hydrogen phosphide cumene is 1h
-1.
Logistics I enters knockout tower T-201, and after rectifying, tower top obtains logistics II, and tower reactor obtains logistics III.The operational condition of knockout tower T-201 is: absolute pressure of top of the tower is 0.04MPa, and tower top temperature is 120 ℃, and tower reactor temperature is 140 ℃.
Logistics II enters hexanaphthene tower T-202, and after rectifying separation, tower top obtains hexanaphthene, and tower reactor obtains logistics IV.The operational condition of hexanaphthene tower T-202 is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and tower reactor temperature is 125 ℃.
Logistics IV enters HEO tower T-203, and after rectifying separation, tower top obtains product HEO, and tower reactor obtains solvent isopropyl benzene.The operational condition of HEO tower T-203 is: absolute pressure of top of the tower is 0.05MPa, and tower top temperature is 120 ℃, and tower reactor temperature is 140 ℃.
Logistics III enters hydrogenator R-201, and remaining hydrogen phosphide cumene is carried out to hydrotreatment, obtains logistics V after reaction.Hydrogenator R-201 filling 10kg Pd/C catalyzer, reaction pressure is 0.8Mpa, temperature of reaction is 70 ℃, H
2with the mol ratio of residual hydrogen peroxide isopropyl benzene be 10: 1, air speed 1.5h
-1.
Logistics V enters α, alpha-alpha-dimethyl benzylalcohol tower T-204, and after rectifying separation, tower top obtains solvent isopropyl benzene, and tower reactor obtains product α, alpha-alpha-dimethyl benzylalcohol.The operational condition of T-204 tower is: absolute pressure of top of the tower is 0.04MPa, and tower top temperature is 140 ℃, and tower reactor temperature is 180 ℃.
Using the analytical results of reaction times as between 48～96h as the evaluation result of whole device, and evaluation result is in Table 1.
[embodiment 16～23]
The method examination of [embodiment 15] for catalyzer prepared by [embodiment 2～9], just reaction conditions is different.Concrete reaction conditions and evaluation result are in Table 1.
[embodiment 24]
The moulding Ti-MCM-41 catalyzer finished product that 20.0kg is prepared by [embodiment 10] is loaded in stainless steel fixed-bed reactor R-101, purity is that the tetrahydrobenzene (all the other are hexanaphthene) of 95.0wt% and the cumene solution of the hydrogen phosphide cumene that concentration is 35.0wt% are driven in reactor by volume pump respectively, obtains logistics I after reaction.The temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 90 ℃, and reaction pressure is 1.0MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 0.85: 1, and the weight space velocity of hydrogen phosphide cumene is 2.0h
-1.
The rectifying separation of logistics I is with [embodiment 15], and when just logistics III enters hydrogenator R-201 remaining hydrogen phosphide cumene is carried out to hydrotreatment, catalyzer used is Raney's nickel, and reaction pressure is 1.0MPa, and temperature of reaction is 75 ℃, H
2with the mol ratio of residual hydrogen peroxide isopropyl benzene be 10: 1, air speed 1.0h
-1.Evaluation result is in Table 1.
[embodiment 25～28]
The method examination of [embodiment 24] for catalyzer prepared by [embodiment 11～14], just reaction conditions is different.Concrete reaction conditions and evaluation result are in Table 1.
[comparative example 1]
In a 100ml there-necked flask with reflux condensate device and NaOH aqueous solution absorption unit, add 41.0g tetrahydrobenzene (HE) and 36.0ml distilled water, with water bath with thermostatic control, be heated to 60 ℃, drive magnetic stirring apparatus, in 2.0h, pass into continuously 71.0g Cl
2react Cl
2after passing into, continue stirring reaction 30min.The temperature to 90 ℃ that raises subsequently adds 38.0gCa (OH) in reactor
2and supplement 20.0ml distilled water simultaneously and continue reaction 1.5h, can think that reaction finishes.Take out reaction product and analyze, the epoxy cyclohexane (HEO) that draws by analysis generation is 39.5g, produces containing 57.0gCaCl simultaneously
2the about 120.0g of waste water.HE transformation efficiency and HEO yield are respectively 90.5% and 80.7%.
[comparative example 2]
Take the hydrogen phosphide cumene solution (CHP of 60.8g50 (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.CHP transformation efficiency and DMBA yield are respectively 89.5% and 77.0%.
Claims (3)
1. 2-epoxy cyclohexane and a α, the co-production of alpha-alpha-dimethyl benzylalcohol, comprises the following steps:
A) take tetrahydrobenzene 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 20～150 ℃, reaction pressure is 0.1～10.0MPa, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 0.1～1: 1, the weight percentage of hydrogen phosphide cumene in solvent is 1.0～90%, and the weight space velocity of hydrogen phosphide cumene is 0.01～20 hour
-1under condition, in reactor, reaction raw materials and catalyzer contact reacts obtain stream I; Wherein said catalyzer is selected from unformed Ti/SiO
2; In catalyzer, titanium content is catalyst weight 0.5～5%;
B) stream I enters knockout tower, and after rectifying, tower top obtains stream I I, and tower reactor obtains stream I II;
C) stream I I enters hexanaphthene tower, and after rectifying separation, tower top obtains hexanaphthene, and tower reactor obtains stream I V;
D) stream I V enters HEO tower, and after rectifying separation, tower top obtains product HEO, and tower reactor obtains solvent;
E) stream I II enters hydrogenator, obtains logistics V after reaction;
F) logistics V enters α, alpha-alpha-dimethyl benzylalcohol tower, and after rectifying separation, tower top obtains solvent, and tower reactor obtains product α, alpha-alpha-dimethyl benzylalcohol;
Before described catalyzer is used, at 50～350 ℃, with the organic silicon solution being dissolved in organic solvent, process 1～24 hour, or 50～350 ℃ under gas phase condition by organosilicon steam treatment 1～24 hour, wherein organosilicon is selected from least one in halosilanes, silazane or silylamine, and organosilicon consumption is catalyst weight 1～50%;
Described halosilanes is selected from trimethylchlorosilane, and described silazane is selected from least one in hexamethyldisilazane or 1,1,3,3-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;
The described non-polar organic solvent that reaction system is to inertia is selected from isopropyl benzene.
2. according to claim 11,2-epoxy cyclohexane and α, the co-production of alpha-alpha-dimethyl benzylalcohol, it is characterized in that temperature of reaction is 40～130 ℃, reaction pressure is 0.1～6.0MPa, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 0.3～1: 1, and the weight percentage of hydrogen phosphide cumene in solvent is 5～50%, and the weight space velocity of hydrogen phosphide cumene is 0.1～10 hour
-1.
3. HEO and α according to claim 1, the co-production of alpha-alpha-dimethyl benzylalcohol, is characterized in that described reactor is fixed-bed reactor or paste state bed reactor.
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| CN102766115B (en) * | 2012-07-03 | 2014-08-13 | 中国平煤神马能源化工集团有限责任公司 | Method for producing epoxycyclohexane with fixed bed reactor |
| CN104437636B (en) * | 2013-09-24 | 2018-08-17 | 中国石油化工股份有限公司 | Titaniferous porous silica Si catalyst, preparation method and its usage |
| CN105315233B (en) * | 2014-07-03 | 2018-06-08 | 中国石油化工股份有限公司 | The production method of epoxy butane |
| CN105367518B (en) * | 2014-08-27 | 2018-07-17 | 中国石油化工股份有限公司 | The method of coproduction epoxides and cumyl peroxide |
| CN107445796B (en) * | 2017-08-22 | 2020-07-28 | 岳阳昌德环境科技有限公司 | Method for co-producing dimethyl benzyl alcohol and 1, 2-pentanediol |
| CN110372639A (en) * | 2019-07-16 | 2019-10-25 | 中国石油化工股份有限公司 | A kind of method that Titanium Sieve Molecular Sieve prepares 7-oxa-bicyclo[4.1.0 |
| JP7284692B2 (en) * | 2019-11-26 | 2023-05-31 | 住友化学株式会社 | Method for producing aromatic alcohol |
| CN113636991A (en) * | 2021-08-13 | 2021-11-12 | 中国天辰工程有限公司 | Synthesis method of epoxy cyclohexane |
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