CN102295624B - Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane - Google Patents
Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane Download PDFInfo
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Abstract
The invention relates to a method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane. 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 and the problems that the accumulated cyclohexane in the raw material affects the reaction efficiency and affects normal reaction. 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 isoxidized into the 1,2-epoxy cyclohexane; and meanwhile, the cyclohexane and the cyclohexene are efficiently separated by adopting an extractive rectification technology. 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, the alpha, alpha-dimethyl benzyl alcohol and the cyclohexane.
Description
Technical field
The present invention relates to a kind of coproduction HEO, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene.
Background technology
1, the 2-epoxy cyclohexane is a kind of important organic synthesis intermediate, because of the epoxy group(ing) on its molecular structure very active, can with the reactions such as amine, phenol, alcohol, carboxylic acid, 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.The agricultural chemicals propargite synthetic with HEO is that higher effective and lower toxic pesticide is welcome by the peasant deeply.The hexanedial synthetic by HEO is widely used in oil production and process hides.In addition, as epoxide resin reactive diluent, on 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 simultaneously to use chlorine, this is so that raw material supply and safe having problems.In addition, can also from the waste liquid of cyclohexane oxidation hexalin processed and pimelinketone, extract the recovery HEO.But because waste liquid quantity is limited, its scale is difficult to improve, and can not need by satisfying the market.CN1880310 discloses a kind of employing quaternary ammonium salt phosphor-tungstic heteropoly acid and has made catalyzer, prepares the method for HEO with the hydrogen peroxide oxidation tetrahydrobenzene.But because catalyst separating difficulty, turnover rate are higher, and the HEO cost that the reasons such as catalyzer and hydrogen peroxide price height cause adopting this technology to produce is high.
α, alpha-alpha-dimethyl benzylalcohol are the important source material of preparation dicumyl peroxide (DCP).DCP is considered to industrial monosodium glutamate, and it can make polymkeric substance have three-dimensional structure as linking agent, greatly improves physical property; Be used for poly polymerization, its product can be used as the exterior of cable; Be used for the EVA crosslinked foam, can produce the foam materials with fine pores; Be used for the crosslinked of EPM, EPDM, can improve insulativity, processibility and the thermotolerance of product.It also is the excellent vulcanizing agent of natural rubber, synthetic rubber and polyvinyl resin.
Industrial at present, α, alpha-alpha-dimethyl benzylalcohol are under 60～65 ℃, use Na
2SO
3Or Na
2The S aqueous solution is that reductive agent reduction hydrogen phosphide cumene prepares.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 also will produce a large amount of unpleasant poisonous hydrogen sulfide up to 3.4 ten thousand mg/L 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 the alkene selective oxidation prepares epoxide.
Document US 3923843 and US 4367342 disclose amorphous silica take titaniferous as catalyzer, and hydrogen peroxide ethylbenzene (EBHP) can be propylene oxide and by-product α-methylbenzylalcohol with Selective Oxidation of Propylene.This patent just reacts hydrogen peroxide ethylbenzene and propylene to produce propylene oxide, and the α-methylbenzylalcohol of by-product is not mentioned take hydrogen phosphide cumene as oxygenant and come cyclohexene oxide through the standby vinylbenzene of further Dehydration.
Document CN1500004A and CN 1248579A disclose take hydrogen phosphide cumene (CHP) or hydrogen peroxide ethylbenzene (EBHP) as 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, and the preparation technology of alpha-alpha-dimethyl benzylalcohol and other alkene and hydrogen phosphide cumene react to prepare α, the process of alpha-alpha-dimethyl benzylalcohol.
In sum, in the 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.
In addition, owing to being subjected to the restriction of tetrahydrobenzene production technique, always contain a certain amount of hexanaphthene in the tetrahydrobenzene product of technical grade.Along with tetrahydrobenzene and the carrying out of hydrogen phosphide cumene catalytic oxidation-reduction reaction and recycling of raw material tetrahydrobenzene, hexanaphthene is gradually accumulation in system.This not only affects reaction efficiency but also can affect normally carrying out of reaction.
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, production cost be high, and the problem that cumulative effect reaction efficiency, impact reaction are normally carried out in system of the hexanaphthene in the raw material, provide a kind of new coproduction HEO, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene.The method can obtain HEO, α simultaneously, alpha-alpha-dimethyl benzylalcohol and hexanaphthene product, and it is high to have a catalyst activity and selectivity, and reaction conditions is gentle, and is pollution-free, the characteristics 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 coproduction HEO, α, and the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene may further comprise the steps:
A) the raw material tetrahydrobenzene obtains logistics I with the catalyzer contact reacts with the hydrogen phosphide cumene that is dissolved in the solvent in reactor;
B) the logistics I enters knockout tower, and after rectifying separation, cat head obtains the logistics II, obtains the logistics III at the bottom of the tower;
C) the logistics II enters thick HEO tower, and after rectifying separation, cat head obtains the logistics IV, obtains the logistics V at the bottom of the tower;
D) the logistics IV enters the hexanaphthene tower, and behind separation of extractive distillation, cat head obtains hexanaphthene, obtains the logistics VI at the bottom of the tower;
E) the logistics VI enters the tetrahydrobenzene tower, and behind separation of extractive distillation, cat head obtains tetrahydrobenzene, is circulated to reactor inlet; Be extracted agent at the bottom of the tower, be circulated to hexanaphthene tower middle part;
F) the logistics V enters smart HEO tower, and after rectifying separation, cat head obtains HEO, obtains solvent at the bottom of the tower;
G) the logistics III enters α, alpha-alpha-dimethyl benzylalcohol tower, and after rectifying separation, cat head obtains solvent, and tower reactor obtains α, alpha-alpha-dimethyl benzylalcohol.
In the technique scheme, described solvent preferred version is for being the nonpolar organic compound of inertia to reaction system, more preferably scheme is to be selected from least a in benzene,toluene,xylene, ethylbenzene, diethylbenzene, isopropyl benzene, diisopropylbenzene(DIPB), normal butane, Trimethylmethane, pentane, normal hexane, hexanaphthene, heptane, octane, nonane, decane, undecane hydrocarbon or the dodecane hydrocarbon, and most preferably scheme is for being selected from isopropyl benzene.Reaction conditions preferable range in the reactor is: 20～150 ℃ of temperature of reaction, reaction pressure 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
-1More preferably the scope 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
-1Described catalyzer preferred version is for being 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 a, more preferably scheme is for being selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 or unformed Ti/SiO
2In at least a; Most preferably scheme is for being selected from Ti-HMS, Ti-MCM-41 or unformed Ti/SiO
2In at least a.The titanium content preferable range is 0.1～20% of catalyst weight in the catalyzer, and more preferably scope is 0.2～10% of catalyst weight, and most preferred range is 0.5～5% of catalyst weight.The operational 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 the tower reactor temperature is 120～160 ℃; More preferably scope is: absolute pressure of top of the tower is 0.03～0.05MPa, and tower top temperature is 90～130 ℃, and the tower reactor temperature is 130～150 ℃.The operational condition of thick HEO tower is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 50～90 ℃, and the tower reactor temperature is 100～140 ℃; More preferably scope is: absolute pressure of top of the tower is 0.05～0.07MPa, and tower top temperature is 70～85 ℃, and the tower reactor temperature is 110～130 ℃.The operational 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 the tower reactor temperature is 100～150 ℃; More preferably scope is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 70～85 ℃, and the tower reactor temperature is 120～140 ℃; Described extraction agent is preferably from N,N-dimethylacetamide.The operational condition of tetrahydrobenzene tower is: absolute pressure of top of the tower is 0.03～0.1MPa, and tower top temperature is 65～95 ℃, and the tower reactor temperature is 120～155 ℃; More preferably scope is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 70～90 ℃, and the tower reactor temperature is 130～145 ℃.The operational condition of essence HEO tower is: absolute pressure of top of the tower is 0.02～0.08MPa, and tower top temperature is 100～140 ℃, and the tower reactor temperature is 120～160 ℃; More preferably scope is: absolute pressure of top of the tower is 0.03～0.07MPa, and tower top temperature is 110～130 ℃, and the tower reactor temperature is 130～150 ℃.α, the operational 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 the tower reactor temperature is 150～210 ℃; More preferably scope is: absolute pressure of top of the tower is 0.02～0.05MPa, and tower top temperature is 130～160 ℃, and the tower reactor temperature is 160～200 ℃.Before catalyzer used, preferably with being dissolved in the organic silicon solution in the organic solvent or using the organosilicon steam treatment under gas phase condition, silanization temperature preferable range was 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.The organosilicon preferred version is to be selected from least a in halosilanes, silazane or the silylamine; Wherein said halosilanes preferred version is to be selected from least a in 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 the 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-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1, at least a in 3,3-tetramethyl-disilazane or 1, the 3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1, at least a in 1,3, the 3-tetramethyl-disilazane; Described silylamine is selected from least a 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 the N-trimethyl silyl diethylamide.The organosilicon consumption is preferably 0.1～100% of catalyst weight, and more preferably scope is 1～50%.Described reactor preferred version is for being selected from fixed-bed reactor or paste state bed reactor.
Catalyzer of 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 a, wherein the content of titanium is 0.1～20% of catalyst weight in the catalyzer.This titaniferous porous silica catalyzer is synthetic for carrying titanium by direct synthetic or rear grafting, has the meso-hole structure feature, such as Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1; Or have the macroporous structure feature, such as unformed Ti/SiO
2This 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 the 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 the reductive agent reduction, the reaction mechanism of alpha-alpha-dimethyl benzylalcohol, but and the reaction characteristics of organic hydroperoxide catalyzed oxidation produce epoxides in the presence of catalyzer, novelty combines the two kinds of reaction mechanisms in ground.Under the reaction conditions of gentleness, porous silica catalyzer at titaniferous makes hydrogen phosphide cumene and tetrahydrobenzene generation redox reaction, wherein hydrogen phosphide cumene is reduced to α, alpha-alpha-dimethyl benzylalcohol, tetrahydrobenzene then is oxidized to 1 simultaneously, the 2-epoxy cyclohexane, catalyst activity is high, good product selectivity.Like this, can produce the fine chemical product of two kinds of high added values by a reaction, meet the atom economy chemical principle.Preferred catalyst of the present invention carries out silanization and processes before use, and the hydroxyl that its surface is existed is converted into the alkyl siloxy, strengthens hydrophobicity, reduces acid.The hydrophobic raising of catalyzer can reduce the polarity oxidation products in the absorption of catalyst surface, also can avoid the loss of active constituent titanium on the 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 the catalyzer that adopts is a kind of typical heterogeneous catalyst, so HEO and α adopting the method to produce do not contain catalyzer in the alpha-alpha-dimethyl benzylalcohol reaction solution, 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 higher tetrahydrobenzene product of purity, so always contain relatively large hexanaphthene in the tetrahydrobenzene product, be generally 5.0 % by weight.Adopt such tetrahydrobenzene to make raw material through after its catalytic oxidation-reduction reaction and recycling, the hexanaphthene amount in the reaction product can accumulate gradually, and this not only affects reaction efficiency but also can affect normally carrying out of reaction.The present invention adopts extraction and distillation technology efficiently hexanaphthene to be separated with tetrahydrobenzene, the tetrahydrobenzene of recovery is recycled, satisfy the reaction process needs, and can obtain highly purified hexanaphthene joint product, improve productivity effect, obtained preferably technique effect.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
Among Fig. 1, R-101 is reactor, and T-201 is knockout tower, and T-202 is thick 1,2-epoxy cyclohexane tower, T-203 are the hexanaphthene tower, and T-204 is the tetrahydrobenzene tower, T-205 is smart HEO tower, and T-206 is α, alpha-alpha-dimethyl benzylalcohol tower, 1 is tetrahydrobenzene (HE), 2 for being dissolved in the hydrogen phosphide cumene (CHP) in the solvent, 3 is hexanaphthene (HA), and 4 is HEO (HEO), 5 is solvent, and 6 is α, alpha-alpha-dimethyl benzylalcohol (DMBA).
Among Fig. 1, raw material tetrahydrobenzene 1 and the hydrogen phosphide cumene 2 that is dissolved in the solvent obtain the logistics I with the catalyzer contact reacts in reactor R-101.The logistics I enters knockout tower T-201, and after rectifying separation, cat head obtains the logistics II, obtains the logistics III at the bottom of the tower.The logistics II enters thick HEO tower T-202, and after rectifying separation, cat head obtains the logistics IV, obtains the logistics V at the bottom of the tower.The logistics IV enters hexanaphthene tower T-203, and behind separation of extractive distillation, cat head obtains hexanaphthene, obtains the logistics VI at the bottom of the tower.The logistics VI enters tetrahydrobenzene tower T-204, and behind separation of extractive distillation, cat head obtains tetrahydrobenzene, is circulated to reactor R-101 entrance, recycles; Be extracted agent at the bottom of the tower, be circulated to hexanaphthene tower T-203 middle part.The logistics V enters smart HEO tower T-205, and after rectifying separation, cat head obtains HEO 4, obtains solvent 5 at the bottom of the tower.The logistics III enters α, alpha-alpha-dimethyl benzylalcohol tower T-206, and after rectifying separation, cat head obtains solvent 5, and tower reactor obtains α, alpha-alpha-dimethyl benzylalcohol 6.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The 30.0kg aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 48.0kg25wt%, and continuously stirring 30min forms solution.Under agitation mentioned solution is joined in the 120.0L aqueous solution that contains the 46.0kg cetyl trimethylammonium bromide subsequently and form clear solution.Above-mentioned mixing solutions is moved in the crystallizing kettle, adds 0.1kgMCM-41 as crystal seed, in 100 ℃ of static crystallization 3 days.Product after the crystallization is after washing, filtering, and in 100 ℃ of oven dry 24h, 550 ℃ of roasting 6h namely get the support of the catalyst with MCM-41 constitutional features.Adopt traditional extruded moulding technology that the powder MCM-41 support of the catalyst of above-mentioned preparation is processed into the bar that diameter is 1.5mm, then through 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h namely get the MCM-41 carrier of moulding.
In reactor, add and contain 8.0kgTiCl
4The 100L cumene solution, the support of the catalyst of above-mentioned preparation is joined in the reactor, under slowly stirring and refluxing, rising temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent.Add distilled water 60L after being cooled to 90 ℃ and stir 30min, the temperature to 110 that then raises ℃ evaporating water namely makes the Ti-MCM-41 catalyst Precursors.
In another reactor, add the 100L cumene solution contain the 4.0kg hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 20.0kg is joined in the reactor, under slowly stirring and refluxing, rising temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent namely 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 3.5%.
[embodiment 2]
The 30.0Kg aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 48.0kg25wt%, and continuously stirring 30min forms solution.Under agitation mentioned solution is joined in the 120.0L aqueous solution that contains the 46.0kg cetyl trimethylammonium bromide subsequently and form clear solution.Slowly be added drop-wise in the above-mentioned mixing solutions and continuation stirring 30min at lower 4.8Kg tetrabutyl titanate of rapid stirring.The mixing solutions of above-mentioned siliceous and titanium is moved in the crystallizing kettle, add 0.1kg Ti-MCM-41 as crystal seed, in 100 ℃ of static crystallization 3 days, namely make the Ti-MCM-41 catalyst Precursors.
In another reactor, add and contain 3.0kg1,1,3, the 100L cumene solution of 3-tetramethyl-disilazane joins the catalyst Precursors of the above-mentioned preparation of 20.0kg in the reactor, at rapid stirring with under refluxing, rising temperature to 150 ℃, and under this temperature, react 4h.Then under this temperature, 1,1,3 of evaporated in vacuo remnants, 3-tetramethyl-disilazane and isopropyl benzene solvent namely 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 2.1%.
[embodiment 3]
Method by [embodiment 1] makes the Ti-MCM-41 catalyzer, just catalyzer is not carried out silanization and processes.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 3.7%.
[embodiment 4]
In room temperature with under stirring, the 30.0kg cetylamine joined contain 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 will be dissolved in the 130.0kg tetraethoxy in the 60L ethanol and be dissolved in the 20L ethanol joins in the above-mentioned mixing solutions simultaneously, crystallization 24h behind the stirring 30min.Then filter the gained decorating film, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is namely got the Ti-HMS catalyst Precursors.
By the method for [embodiment 2] catalyzer is carried out silanization and process, just silylating reagent adopts trimethylchlorosilane, and its consumption is 8kg, 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]
In room temperature with under stirring, the 30.0kg cetylamine joined contain 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 that will be dissolved in the 60L ethanol joins in the above-mentioned mixing solutions, crystallization 24h behind the stirring 30min.Then filter the gained decorating film, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is namely got the support of the catalyst with HMS constitutional features.Adopt traditional extruded moulding technology that the powder MCM-41 support of the catalyst of above-mentioned preparation is processed into the bar that diameter is 1.5mm, then through 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h namely get the HMS carrier of moulding.
The HMS carrier of moulding is carried titanium and silanization is processed by the method for [embodiment 1], just the consumption of silylating reagent is 5kg, makes the Ti-HMS catalyzer through the 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 2.8%.
[embodiment 6]
Method by [embodiment 5] makes the Ti-HMS catalyzer, just catalyzer is not carried out silanization and processes.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 3.0%.
[embodiment 7]
In room temperature with under stirring, the 8.6kg tetrabutyl titanate is joined the ethanolic soln that forms tetrabutyl titanate in the 40L ethanol, commercially available silica gel (80-120 order, specific surface area 340m that the 40.0Kg drying treatment is crossed
2G, pore volume 0.71cm
3/ g, mean pore size
) join in the 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, with washing with alcohol filtrate three times.Solid 12h in air atmosphere after 110 ℃ of above-mentioned filtrations of oven dry at 600 ℃ of roasting 4h, namely gets catalyst Precursors Ti/SiO
2
By the method for [embodiment 2] catalyzer is carried out silanization and process, just the consumption of silylating reagent is 2kg, makes the Ti/SiO that processes 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]
Adopt traditional forming technique with commercially available silica gel (80-120 order, specific surface area 340m
2/ g, pore volume 0.71cm
3/ g, mean pore size
) be processed into the moulding SiO of suitable fixed bed applications
2Carrier.With 40.0kg moulding SiO
2Carrier is immersed in the 120L octane solvent.Under stirring and nitrogen atmosphere, will be dissolved with 4.8kgTiCl
440L octane mixture join in the said mixture, be warming up to 100 ℃ after constant temperature stirring and refluxing 2h, then rising temperature to 150 ℃ solvent evaporated under vacuum condition.The sample of above-mentioned acquisition is put in the quartz tube reactor, in nitrogen atmosphere, rising temperature to 700 ℃, and at this roasting temperature 2h, reduce the temperature to 300 ℃ after, pass into saturated steam and process 2h, nitrogen purging 2h.Namely make preformed catalyst parent Ti/SiO
2
The method of [embodiment 1] of pressing is to the Ti/SiO of moulding
2Catalyst Precursors carries out silanization to be processed, and just silylating reagent adopts trimethylchlorosilane, namely makes the moulding Ti/SiO that processes through silanization
2The catalyzer finished product.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 1.5%.
[embodiment 9]
Method by [embodiment 7] prepares Ti/SiO
2Catalyzer does not just carry out silanization to it and processes.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 10]
20.0kg is loaded among the stainless steel fixed-bed reactor R-101 by the moulding Ti-MCM-41 catalyzer finished product of [embodiment 1] preparation, purity is that the tetrahydrobenzene (all the other are hexanaphthene) of 95.0wt% and cumene solution that concentration is the hydrogen phosphide cumene of 30.0wt% are driven in the reactor by volume pump respectively, obtains the logistics I after the reaction.The temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 90 ℃, and reaction pressure is 0.5MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 2: 1, and the weight space velocity of hydrogen phosphide cumene is 2.0h
-1
The logistics I enters knockout tower T-201, and after rectifying, cat head obtains the logistics II, and tower reactor obtains the 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 the tower reactor temperature is 140 ℃.
The logistics II enters thick HEO tower T202, and after rectifying separation, cat head obtains the logistics IV, obtains the logistics V at the bottom of the tower.The operational condition of thick HEO tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and the tower reactor temperature is 120 ℃.
The logistics IV enters hexanaphthene tower T203, and extraction agent is N,N-dimethylacetamide, and behind extracting rectifying, cat head obtains hexanaphthene, obtains the logistics VI at the bottom of the tower.The operational condition of hexanaphthene tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and the tower reactor temperature is 130 ℃.
The logistics VI enters tetrahydrobenzene tower T204, and after rectifying separation, cat head obtains tetrahydrobenzene, is circulated to reactor inlet; Be extracted the agent N,N-dimethylacetamide at the bottom of the tower, be circulated to hexanaphthene tower middle part.The operational condition of tetrahydrobenzene tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 80 ℃, and the tower reactor temperature is 140 ℃.
The logistics V enters smart HEO tower T205, and after rectifying separation, cat head obtains HEO, obtains the solvent isopropyl benzene at the bottom of the tower.The operational condition of essence HEO tower is: absolute pressure of top of the tower is 0.05MPa, and tower top temperature is 120 ℃, and the tower reactor temperature is 140 ℃.
The logistics III enters α, alpha-alpha-dimethyl benzylalcohol tower T206, and after rectifying separation, cat head obtains the solvent isopropyl benzene, and tower reactor obtains α, alpha-alpha-dimethyl benzylalcohol.α, the operational condition of alpha-alpha-dimethyl benzylalcohol tower is: absolute pressure of top of the tower is 0.04MPa, and tower top temperature is 140 ℃, and the tower reactor temperature is 180 ℃.
Take the reaction times as the evaluation result of the analytical results between 48～96h as whole device, evaluation result sees Table 1.
[embodiment 11]
Be 20.0kg by the Ti-MCM-41 catalyst loading of [embodiment 2] preparation in the stainless steel cauldron R-101 with agitator with initial loadings, purity is that the tetrahydrobenzene (all the other are hexanaphthene) of 95.0wt% and cumene solution that concentration is the hydrogen phosphide cumene of 30.0wt% are driven in the reactor by volume pump respectively, obtains the logistics I after the reaction.The temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 80 ℃, and reaction pressure is 1.0MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 6: 1, and the weight space velocity of hydrogen phosphide cumene is 1h
-1
The rectifying separation of logistics I is with [embodiment 10].Evaluation result sees Table 1.
[embodiment 12]
By the method for [embodiment 10] catalyzer of [embodiment 3] is carried out performance evaluation, just the concentration of hydrogen phosphide cumene in the solvent isopropyl benzene is 10%, the temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 110 ℃ in the R-101 reactor, reaction pressure is 3.0MPa, and the weight space velocity of hydrogen phosphide cumene is 4.0h
-1Evaluation result sees Table 1.
[embodiment 13]
By the method for [embodiment 11] catalyzer of [embodiment 4] is carried out performance evaluation, just the concentration of hydrogen phosphide cumene in the solvent isopropyl benzene is 25%, temperature of reaction is 100 ℃ in the R-101 reactor, reaction pressure is 2.0MPa, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 8: 1, and the weight space velocity of hydrogen phosphide cumene is 8.0h
-1Evaluation result sees Table 1.
[embodiment 14]
By the method for [embodiment 10] catalyzer of [embodiment 5] is carried out performance evaluation, just the concentration of hydrogen phosphide cumene in the solvent isopropyl benzene is 20.0%, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 1.2: 1.Evaluation result sees Table 1.
[embodiment 15]
By the method for [embodiment 10] catalyzer of [embodiment 6] is carried out performance evaluation, just the temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 70 ℃, and reaction pressure is 5.0Mp, and the weight space velocity of hydrogen phosphide cumene is 0.3h-1.
[embodiment 16]
By the method for [embodiment 11] catalyzer of [embodiment 7] is carried out performance evaluation, just the weight percentage of hydrogen phosphide cumene in the solvent isopropyl benzene is 45%, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 10: 1, and the weight space velocity of hydrogen phosphide cumene is 3h
-1Evaluation result sees Table 1.
[embodiment 17]
By the method for [embodiment 10] catalyzer of [embodiment 8] is carried out performance evaluation, just the temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 95 ℃, reaction pressure is 3.0MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 4: 1, and the weight space velocity of hydrogen phosphide cumene is 1.5h
-1Evaluation result sees Table 1.
[embodiment 18]
By the method for [embodiment 11] catalyzer of [embodiment 9] is carried out performance evaluation, just the temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 115 ℃, reaction pressure is 4.0MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 4: 1, and the weight space velocity of hydrogen phosphide cumene is 6.0h
-1Evaluation result sees Table 1.
Table 1
| Embodiment | CHP transformation efficiency (%) | HEO yield (% is to CHP) | DMBA yield (% is to CHP) | HA yield (%) |
| Embodiment 10 | 99.5 | 94.5 | 92.3 | 95.6 |
| Embodiment 11 | 99.0 | 94.1 | 92.0 | 95.3 |
| Embodiment 12 | 97.7 | 91.5 | 90.2 | 95.2 |
| Embodiment 13 | 99.2 | 93.9 | 91.5 | 94.9 |
| Embodiment 14 | 99.0 | 93.4 | 91.3 | 95.0 |
| Embodiment 15 | 95.5 | 89.1 | 88.5 | 95.2 |
| Embodiment 16 | 98.0 | 92.5 | 91.0 | 95.1 |
| Embodiment 17 | 98.6 | 93.0 | 91.3 | 94.7 |
| Embodiment 18 | 98.0 | 88.4 | 87.1 | 95.0 |
[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, be heated to 60 ℃ with water bath with thermostatic control, drive magnetic stirring apparatus, in 2.0h, pass into continuously 71.0g Cl
2React Cl
2Pass into complete after, continue stirring reaction 30min.The temperature to 90 that raises subsequently ℃ adds 38.0gCa (OH) in reactor
2And replenish simultaneously 20.0ml distilled water 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 simultaneously to contain 57.0gCaCl
2The about 120.0g of waste water.HE transformation efficiency and HEO yield are respectively 90.5% and 80.7%.
[comparative example 2]
Take by weighing the hydrogen phosphide cumene solution (CHP of 60.8g 50 (weight) %, isopropyl benzene is solvent) join in three mouthfuls of glass flask of 200ml with the backflow prolong, during rising temperature to 65 ℃, start magnetic agitation, slowly with the Na of 14.5g 30 (weight) %
2The S aqueous solution is added drop-wise in the 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 simultaneously to contain 7.5gNa
2SO
4And Na
2The waste water of S is 18.0g approximately.CHP transformation efficiency and DMBA yield are respectively 89.5% and 77.0%.
Claims (1)
1. a coproduction HEO, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene may further comprise the steps: the 30.0kg aerosil is joined in the tetramethylammonium hydroxide aqueous solution of 48.0kg25wt%, and continuously stirring 30min forms solution; Under agitation mentioned solution is joined in the 120.0L aqueous solution that contains the 46.0kg cetyl trimethylammonium bromide subsequently and form clear solution; Above-mentioned mixing solutions is moved in the crystallizing kettle, adds 0.1kg MCM-41 as crystal seed, in 100 ℃ of static crystallization 3 days; Product after the crystallization is after washing, filtering, and in 100 ℃ of oven dry 24h, 550 ℃ of roasting 6h namely get the support of the catalyst with MCM-41 constitutional features; Adopt traditional extruded moulding technology that the powder MCM-41 support of the catalyst of above-mentioned preparation is processed into the bar that diameter is 1.5mm, then through 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h namely get the MCM-41 carrier of moulding;
In reactor, add and contain 8.0kgTiCl
4The 100L cumene solution, the support of the catalyst of above-mentioned preparation is joined in the reactor, under slowly stirring and refluxing, rising temperature to 150 ℃, and under this temperature, react 4h; Then under this temperature, the TiCl of evaporated in vacuo remnants
4With the isopropyl benzene solvent; Add distilled water 60L after being cooled to 90 ℃ and stir 30min, the temperature to 110 that then raises ℃ evaporating water namely makes the Ti-MCM-41 catalyst Precursors;
In another reactor, add the 100L cumene solution contain the 4.0kg hexamethyldisilazane, the catalyst Precursors of the above-mentioned preparation of 20.0kg is joined in the reactor, under slowly stirring and refluxing, rising temperature to 150 ℃, and under this temperature, react 4h; Then under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent namely 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 3.5%;
The moulding Ti-MCM-41 catalyzer finished product that 20.0kg is prepared as stated above is loaded among the stainless steel fixed-bed reactor R-101, purity is the tetrahydrobenzene of 95.0wt%, all the other are hexanaphthene, with concentration be that the cumene solution of the hydrogen phosphide cumene of 30.0wt% is driven in the reactor by volume pump respectively, obtain stream I after the reaction; The temperature of reaction of tetrahydrobenzene and hydrogen phosphide cumene is 90 ℃, and reaction pressure is 0.5MPa, and the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 2: 1, and the weight space velocity of hydrogen phosphide cumene is 2.0h
-1
Stream I enters knockout tower T-201, and after rectifying, cat head obtains stream I I, and tower reactor obtains stream I II; 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 the tower reactor temperature is 140 ℃;
Stream I I enters thick HEO tower T202, and after rectifying separation, cat head obtains the logistics IV, obtains logistics V at the bottom of the tower; The operational condition of thick HEO tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and the tower reactor temperature is 120 ℃;
The logistics IV enters hexanaphthene tower T203, and extraction agent is N,N-dimethylacetamide, and behind extracting rectifying, cat head obtains hexanaphthene, obtains the logistics VI at the bottom of the tower; The operational condition of hexanaphthene tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and the tower reactor temperature is 130 ℃;
The logistics VI enters tetrahydrobenzene tower T204, and after rectifying separation, cat head obtains tetrahydrobenzene, is circulated to reactor inlet; Be extracted the agent N,N-dimethylacetamide at the bottom of the tower, be circulated to hexanaphthene tower middle part; The operational condition of tetrahydrobenzene tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 80 ℃, and the tower reactor temperature is 140 ℃;
Logistics V enters smart HEO tower T205, and after rectifying separation, cat head obtains HEO, obtains the solvent isopropyl benzene at the bottom of the tower; The operational condition of essence HEO tower is: absolute pressure of top of the tower is 0.05MPa, and tower top temperature is 120 ℃, and the tower reactor temperature is 140 ℃;
Stream I II enters α, alpha-alpha-dimethyl benzylalcohol tower T206, and after rectifying separation, cat head obtains the solvent isopropyl benzene, and tower reactor obtains α, alpha-alpha-dimethyl benzylalcohol; α, the operational condition of alpha-alpha-dimethyl benzylalcohol tower is: absolute pressure of top of the tower is 0.04MPa, and tower top temperature is 140 ℃, and the tower reactor temperature is 180 ℃;
Take the reaction times as the evaluation result of the analytical results between 48～96h as whole device, evaluation result is as follows: the CHP transformation efficiency is 99.5%, take CHP as benchmark, the yield of HEO is 94.5%, take CHP as benchmark, the DMBA yield is 92.3%; The HA yield is 95.6%.
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