CN102295624A - 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
- Publication number
- CN102295624A CN102295624A CN2010102081804A CN201010208180A CN102295624A CN 102295624 A CN102295624 A CN 102295624A CN 2010102081804 A CN2010102081804 A CN 2010102081804A CN 201010208180 A CN201010208180 A CN 201010208180A CN 102295624 A CN102295624 A CN 102295624A
- Authority
- CN
- China
- Prior art keywords
- tower
- alpha
- hexanaphthene
- epoxy cyclohexane
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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 is oxidized 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 1,2-epoxy cyclohexane, 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 reactions such as amine, phenol, alcohol, carboxylic acid, generate a series of derivatives, can be widely used in fields such as medicine, agricultural chemicals, solidifying agent, softening agent, thinner, tensio-active agent.With 1,2-epoxy cyclohexane synthetic agricultural chemicals propargite is that higher effective and lower toxic pesticide is welcome by the peasant deeply.By 1,2-epoxy cyclohexane synthetic hexanedial is widely used in oil production and process hides.In addition, as epoxide resin reactive diluent, on economy and performance, more have superiority.
1, the major industry production method of 2-epoxy cyclohexane 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 simultaneously, this makes raw material supply and safety have problems.In addition, can also from the waste liquid of cyclohexane oxidation system hexalin and pimelinketone, extract and reclaim 1, the 2-epoxy cyclohexane.But because waste liquid quantity is limited, its scale is difficult to improve, and can not satisfy market demand.CN1880310 discloses a kind of employing quaternary ammonium salt phosphor-tungstic heteropoly acid and has made catalyzer, with hydrogen peroxide oxidation tetrahydrobenzene preparation 1, the method for 2-epoxy cyclohexane.But because catalyst separating difficulty, turnover rate are higher, and reasons such as catalyzer and hydrogen peroxide price height cause adopting that this technology produces 1,2-epoxy cyclohexane cost height.
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, improves rerum natura greatly; Be used for poly polymerization, its product can be used as the outer dress of cable; Be used for the EVA crosslinked foam, can produce 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 technology produces a large amount of waste water, and 1 ton of DCP of every production will produce 2.5 tons of reductive sulfur-containing waste waters, and COD also will produce a large amount of unpleasant deleterious 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 technology 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.
It is catalyzer that document US 3923843 and US 4367342 disclose with titaniferous amorphous silica, and hydrogen peroxide ethylbenzene (EBHP) can be propylene oxide and by-product α-Jia Jibianchun with Selective Oxidation of Propylene.This patent is just reacted hydrogen peroxide ethylbenzene and propylene and is produced propylene oxide, and the α-Jia Jibianchun of by-product does not mention with the hydrogen phosphide cumene being that oxygenant comes cyclohexene oxide through further dehydration preparation vinylbenzene.
It is oxygenant that document CN1500004A and CN 1248579A disclose with hydrogen phosphide cumene (CHP) or hydrogen peroxide ethylbenzene (EBHP), prepares 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 and prepare α, the process of alpha-alpha-dimethyl benzylalcohol.
In sum, also unexposed coproduction 1 in the prior art, 2-epoxy cyclohexane and α, the method of alpha-alpha-dimethyl benzylalcohol, and produce 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.
In addition, owing to be 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 accumulation gradually in system.This not only influences reaction efficiency but also can influence 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 height, and the problem that cumulative effect reaction efficiency, influence reaction are normally carried out in system of the hexanaphthene in the raw material, provide a kind of new coproduction 1,2-epoxy cyclohexane, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene.This method can obtain 1 simultaneously, 2-epoxy cyclohexane, α, and alpha-alpha-dimethyl benzylalcohol and hexanaphthene product, and have catalyst activity and selectivity height, and the reaction conditions gentleness, 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 1, and 2-epoxy cyclohexane, α, 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 enter thick 1,2-epoxy cyclohexane tower, 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 after extracting rectifying separated, cat head obtained hexanaphthene, obtains the logistics VI at the bottom of the tower;
E) the logistics VI enters the tetrahydrobenzene tower, and after extracting rectifying separated, cat head obtained tetrahydrobenzene, is circulated to reactor inlet; Obtain extraction agent at the bottom of the tower, be circulated to hexanaphthene tower middle part;
F) the logistics V enters essence 1,2-epoxy cyclohexane tower, and after rectifying separation, cat head obtains 1, and the 2-epoxy cyclohexane 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 the tower still obtains α, alpha-alpha-dimethyl benzylalcohol.
In the technique scheme, described solvent preferred version is for to be the inert nonpolar organic compound 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 a catalyst weight in the catalyzer, and more preferably scope is 0.2～10% of a catalyst weight, and most preferred range is 0.5～5% of a 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 tower still 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 tower still temperature is 130～150 ℃.Thick 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 50～90 ℃, and tower still 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 tower still 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 tower still 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 tower still 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 tower still 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 tower still temperature is 130～145 ℃.Essence 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.02～0.08MPa, and tower top temperature is 100～140 ℃, and tower still 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 tower still 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 tower still 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 tower still temperature is 160～200 ℃.Before catalyzer uses, be 0～400 ℃ with being dissolved in the organic silicon solution in the organic solvent or using organosilicon steam treatment, silanization temperature preferable range down in gas phase condition preferably, 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-1,1,3,3-tetramethyl-disilazane or 1, at least a in the 3-phenylbenzene tetramethyl-disilazane, more preferably scheme is for being selected from hexamethyldisilazane or 1,1,3, at least a in 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 a 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 back grafting, has the meso-hole structure feature, as Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15, Ti-KIT-1, Ti-TUD-1; Or have the macroporous structure feature, 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, on titaniferous porous silica catalyzer, make 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 height, good product selectivity.Like this, can produce the fine chemical product of two kinds of high added values, meet the atom economy chemical principle by a reaction.Preferred catalyst of the present invention carries out silanization and handles 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 absorption of polarity oxidation products at 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 unlike two chlorohydrinations productions 1, the 2-epoxy cyclohexane needs chlorine to make raw material like that, so do not have sulfur-bearing, chlorine-contained wastewater and corresponding waste residue to produce, does not have problem of environmental pollution.Because the catalyzer that adopted is a kind of typical heterogeneous catalyst, so, this method of employing produce 1,2-epoxy cyclohexane and α do not contain catalyzer in the alpha-alpha-dimethyl benzylalcohol reaction solution, product purity height, good product quality.
In addition, in industrial tetrahydrobenzene raw material,, be difficult to obtain the higher tetrahydrobenzene product of purity,, be generally 5.0 weight % so always contain relatively large hexanaphthene in the tetrahydrobenzene product because the boiling point of hexanaphthene and tetrahydrobenzene is very approaching.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 influences reaction efficiency but also can influence 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 better technical effect.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Among Fig. 1, R-101 is a reactor, and T-201 is a 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 an essence 1, and 2-epoxy cyclohexane tower, T-206 are 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 1,2-epoxy cyclohexane (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.It is thick 1 that the logistics II enters, 2-epoxy cyclohexane 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 after extracting rectifying separated, cat head obtained hexanaphthene, obtains the logistics VI at the bottom of the tower.The logistics VI enters tetrahydrobenzene tower T-204, and after extracting rectifying separated, cat head obtained tetrahydrobenzene, is circulated to reactor R-101 inlet, recycles; Obtain extraction agent at the bottom of the tower, be circulated to hexanaphthene tower T-203 middle part.The logistics V enters essence 1,2-epoxy cyclohexane tower T-205, and after rectifying separation, cat head obtains 1, and 2-epoxy cyclohexane 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 the tower still 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 above-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, in 100 ℃ of static crystallization 3 days as crystal seed.Product after the crystallization is after washing, filtering, and in 100 ℃ of oven dry 24h, 550 ℃ of roasting 6h promptly 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, through 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h promptly get the MCM-41 carrier of moulding then.
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, elevated 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, elevated temperature to 110 ℃ evaporating water promptly makes the Ti-MCM-41 catalyst Precursors then.
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, elevated temperature to 150 ℃, and under this temperature, react 4h.Under this temperature, the hexamethyldisilazane of evaporated in vacuo remnants and isopropyl benzene solvent promptly make the Ti-MCM-41 catalyzer of handling through silanization then.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have 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 above-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 following 4.8Kg tetrabutyl titanate of quick stirring.The mixing solutions of above-mentioned siliceous and titanium is moved in the crystallizing kettle, add 0.1kg Ti-MCM-41,, promptly make the Ti-MCM-41 catalyst Precursors in 100 ℃ of static crystallization 3 days as crystal seed.
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, under stirring fast and refluxing, elevated 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 promptly make the Ti-MCM-41 catalyzer of handling through silanization.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have 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 handles.XRD, N
2Absorption, FT-IR and UV-Vis characterize and analytical results shows that this material has typical MCM-41 constitutional features and Ti has entered skeleton, have 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.Filter the gained decorating film then, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is promptly got the Ti-HMS catalyst Precursors.
By the method for [embodiment 2] catalyzer is carried out silanization and handle, just silylating reagent adopts trimethylchlorosilane, and its consumption is 8kg, makes the Ti-HMS catalyzer finished product of handling through silanization.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have 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.Filter the gained decorating film then, wash with water.Material after the washing behind 110 ℃ of oven dry 12h, at 600 ℃ of roasting 4h, is promptly 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, through 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h promptly get the HMS carrier of moulding then.
The HMS carrier of moulding is carried titanium and silanization is handled 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 that this material has typical HMS constitutional features and Ti has entered skeleton, have 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 handles.XRD, N
2Absorption, FT-IR, UV-Vis characterize and results of elemental analyses shows that this material has typical HMS constitutional features and Ti has entered skeleton, have 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, at room temperature stir this mixture 2h after-filtration, 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, promptly gets catalyst Precursors Ti/SiO
2
By the method for [embodiment 2] catalyzer is carried out silanization and handle, just the consumption of silylating reagent is 2kg, makes the Ti/SiO that handles through silanization
2Catalyzer.FT-IR, UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have 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, elevated temperature to 150 ℃ solvent evaporated under vacuum condition then.The sample of above-mentioned acquisition is put in the quartz tube reactor, in nitrogen atmosphere, elevated temperature to 700 ℃, and at this roasting temperature 2h, reduce the temperature to 300 ℃ after, feed saturated steam and handle 2h, nitrogen purging 2h.Promptly make preformed catalyst parent Ti/SiO
2
Press the Ti/SiO of the method for [embodiment 1] to moulding
2Catalyst Precursors carries out silanization to be handled, and just silylating reagent adopts trimethylchlorosilane, promptly makes the moulding Ti/SiO that handles through silanization
2The catalyzer finished product.FT-IR, UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have 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 handles.FT-IR, UV-Vis characterize and results of elemental analyses shows that titanium has entered skeleton, have 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 the tower still 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 tower still temperature is 140 ℃.
It is thick 1 that the logistics II enters, 2-epoxy cyclohexane tower T202, and after rectifying separation, cat head obtains the logistics IV, obtains the logistics V at the bottom of the tower.Thick 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.06MPa, and tower top temperature is 75 ℃, and tower still temperature is 120 ℃.
The logistics IV enters hexanaphthene tower T203, and extraction agent is a 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 tower still temperature is 130 ℃.
The logistics VI enters tetrahydrobenzene tower T204, and after rectifying separation, cat head obtains tetrahydrobenzene, is circulated to reactor inlet; Obtain the extraction 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 tower still temperature is 140 ℃.
The logistics V enters essence 1,2-epoxy cyclohexane tower T205, and after rectifying separation, cat head obtains 1, and the 2-epoxy cyclohexane obtains the solvent isopropyl benzene at the bottom of the tower.Essence 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.05MPa, and tower top temperature is 120 ℃, and tower still 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 the tower still 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 tower still temperature is 180 ℃.
With the reaction times be analytical results between 48～96h as the evaluation result of whole device, evaluation result sees Table 1.
[embodiment 11]
With initial loadings is 20.0kg by the Ti-MCM-41 catalyst loading of [embodiment 2] preparation in the stainless steel cauldron R-101 that has agitator, 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 that has reflux condensate device and a 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, feeding 71.0g Cl continuously in 2.0h
2React Cl
2After feeding finishes, continue stirring reaction 30min.Elevated temperature to 90 ℃ adds 38.0gCa (OH) in reactor subsequently
2And replenish 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 generation by analysis 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]
The hydrogen phosphide cumene solution (CHP, isopropyl benzene are solvent) that takes by weighing 60.8g 50 (weight) % joins 200ml and takes back in three mouthfuls of glass flask of stream prolong, during elevated temperature to 65 ℃, starts 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 the α of generation by analysis, the weight of alpha-alpha-dimethyl benzylalcohol (DMBA) is 20.6g, produces simultaneously to contain 7.5gNa
2SO
4And Na
2The about 18.0g of the waste water of S.CHP transformation efficiency and DMBA yield are respectively 89.5% and 77.0%.
Claims (10)
1. coproduction 1,2-epoxy cyclohexane, α, 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 enter thick 1,2-epoxy cyclohexane tower, 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 after extracting rectifying separated, cat head obtained hexanaphthene, obtains the logistics VI at the bottom of the tower;
E) the logistics VI enters the tetrahydrobenzene tower, and after extracting rectifying separated, cat head obtained tetrahydrobenzene, is circulated to reactor inlet; Obtain extraction agent at the bottom of the tower, be circulated to hexanaphthene tower middle part;
F) the logistics V enters essence 1,2-epoxy cyclohexane tower, and after rectifying separation, cat head obtains 1, and the 2-epoxy cyclohexane 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 the tower still obtains α, alpha-alpha-dimethyl benzylalcohol.
2. coproduction 1 according to claim 1,2-epoxy cyclohexane, α, the method of alpha-alpha-dimethyl benzylalcohol and hexanaphthene, it is characterized in that described solvent is for to be the inert nonpolar organic compound to reaction system, reaction conditions 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 (20～1): 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
-1Described 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 a; Titanium content is 0.1～20% of a catalyst weight in the catalyzer;
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 tower still temperature is 120～160 ℃;
Thick 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 50～90 ℃, and tower still temperature is 100～140 ℃;
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 tower still temperature is 100～150 ℃; Described extraction agent is selected 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 tower still temperature is 120～155 ℃;
Essence 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.02～0.08MPa, and tower top temperature is 100～140 ℃, and tower still temperature is 120～160 ℃;
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 tower still temperature is 150～210 ℃.
3. according to the described coproduction 1 of claim 1,2-epoxy cyclohexane, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene is characterized in that described catalyzer is selected from Ti-HMS, Ti-MCM-41, Ti-MCM-48, Ti-SBA-15 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.2～10% of a catalyst weight in the catalyzer.
4. according to the described coproduction 1 of claim 3,2-epoxy cyclohexane, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene is characterized in that described catalyzer is selected from Ti-HMS, Ti-MCM-41 or unformed Ti/SiO
2In at least a; Wherein titanium content is 0.5～5% of a catalyst weight in the catalyzer.
5. according to the described coproduction 1 of claim 1,2-epoxy cyclohexane, α, the method of alpha-alpha-dimethyl benzylalcohol and hexanaphthene, before it is characterized in that catalyzer uses, handled 0.5～48 hour with the organic silicon solution that is dissolved in the organic solvent at 0～400 ℃, or under gas phase condition, use organosilicon steam treatment 0.5～48 hour at 0～400 ℃; Wherein organosilicon is selected from least a in halosilanes, silazane or the silylamine, and the organosilicon consumption is 0.1～100% of a catalyst weight.
6. according to the described coproduction 1 of claim 5,2-epoxy cyclohexane, α, the method of alpha-alpha-dimethyl benzylalcohol and hexanaphthene, before it is characterized in that catalyzer uses, handled 1～24 hour with the organic silicon solution that is dissolved in the organic solvent at 50～350 ℃, or 50～350 ℃ under gas phase condition with organosilicon steam treatment 1～24 hour, the organosilicon consumption is 1～50% of a catalyst weight;
Described halosilanes is 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;
Described silazane is selected from hexamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-two (chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1,3,3-tetramethyl-disilazane or 1, at least a in the 3-phenylbenzene 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.
7. according to the described coproduction 1 of claim 6,2-epoxy cyclohexane, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene, it is characterized in that described halosilanes is selected from trimethylchlorosilane, described silazane is selected from hexamethyldisilazane or 1,1,3, at least a in the 3-tetramethyl-disilazane.
8. according to the described coproduction 1 of claim 2,2-epoxy cyclohexane, α, the method of alpha-alpha-dimethyl benzylalcohol and hexanaphthene is characterized in that described solvent is 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.
9. according to the described coproduction 1 of claim 2,2-epoxy cyclohexane, α, the method of alpha-alpha-dimethyl benzylalcohol and hexanaphthene, it is characterized in that the reaction conditions in the reactor is: temperature of reaction is 40～130 ℃, reaction pressure is 0.1～6.0MPa, the mol ratio of tetrahydrobenzene and hydrogen phosphide cumene is 10～1: 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
The operational condition of knockout tower is: absolute pressure of top of the tower is 0.03～0.05MPa, and tower top temperature is 90～130 ℃, and tower still temperature is 130～150 ℃;
Thick 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.05～0.07MPa, and tower top temperature is 70～85 ℃, and tower still temperature is 110～130 ℃;
The operational condition of hexanaphthene tower is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 70～85 ℃, and tower still temperature is 120～140 ℃;
The operational condition of tetrahydrobenzene tower is: absolute pressure of top of the tower is 0.04～0.08MPa, and tower top temperature is 70～90 ℃, and tower still temperature is 130～145 ℃;
Essence 1, the operational condition of 2-epoxy cyclohexane tower is: absolute pressure of top of the tower is 0.03～0.07MPa, and tower top temperature is 110～130 ℃, and tower still temperature is 130～150 ℃;
α, the operational condition of alpha-alpha-dimethyl benzylalcohol tower is: absolute pressure of top of the tower is 0.02～0.05MPa, and tower top temperature is 130～160 ℃, and tower still temperature is 160～200 ℃.
10. according to the described coproduction 1 of claim 1,2-epoxy cyclohexane, α, the method for alpha-alpha-dimethyl benzylalcohol and hexanaphthene is characterized in that described reactor is fixed-bed reactor or paste state bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102081804A CN102295624B (en) | 2010-06-24 | 2010-06-24 | Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102081804A CN102295624B (en) | 2010-06-24 | 2010-06-24 | Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102295624A true CN102295624A (en) | 2011-12-28 |
| CN102295624B CN102295624B (en) | 2013-10-16 |
Family
ID=45356328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102081804A Active CN102295624B (en) | 2010-06-24 | 2010-06-24 | Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102295624B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315236A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing 3,4-epoxy-1-butylene |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3923843A (en) * | 1972-03-13 | 1975-12-02 | Shell Oil Co | Epoxidation process with improved heterogeneous catalyst |
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| CN101307039A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing epoxide |
-
2010
- 2010-06-24 CN CN2010102081804A patent/CN102295624B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
| US3923843A (en) * | 1972-03-13 | 1975-12-02 | Shell Oil Co | Epoxidation process with improved heterogeneous catalyst |
| CN101307039A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Method for producing epoxide |
Non-Patent Citations (3)
| Title |
|---|
| 李学峰，等: "硅烷化对Ti/HMS分子筛催化性能的影响", 《催化学报》 * |
| 李文忠: "CHP法生产CA和PO的分离模拟与研究", 《天津大学硕士学位论文》 * |
| 李雪峰，等: "硅烷化含钛介孔分子筛催化环己烯环氧化动力学", 《化学反应工程与工艺》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105315236A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Method of producing 3,4-epoxy-1-butylene |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102295624B (en) | 2013-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102295625B (en) | Method for producing 1,2-epoxy cyclohexane and alpha, alpha-dimethyl benzyl alcohol | |
| CN101348472B (en) | Method for preparing epoxide | |
| CN103880783B (en) | Reaction control phase transfer catalyst catalysis preparing epoxypropane by epoxidation of propene method | |
| CN102295627B (en) | Method for preparing 1,2-cyclohexene oxide and dicumyl peroxide | |
| CN101279960B (en) | Preparation of epoxide | |
| CN105367520B (en) | The method for preparing expoxy propane | |
| CN101307039B (en) | Method for producing epoxide | |
| CN1346705A (en) | Process for preparing composite catalyst and its application | |
| CN102295534B (en) | Method for preparing alpha, alpha-dimethyl benzyl alcohol | |
| CN1219596C (en) | Process for prodn. of titanium-contg. silicon oxide catalysts | |
| CN104844493A (en) | Dicumyl peroxide (DCP) and propylene oxied (CHPPO) coproduction method | |
| CN102295626A (en) | Method for preparing 1,2-cyclohexene oxide and alpha, alpha-dimethyl benzyl simultaneously | |
| CN1248579A (en) | Process for preparing propylene oxide | |
| CN102295624B (en) | Method for producing 1,2-epoxy cyclohexane, alpha, alpha-dimethyl benzyl alcohol and cyclohexane | |
| CN109970511B (en) | Method for synthesizing 1, 3-propylene glycol by resource utilization of HPPO byproduct | |
| CN114262341A (en) | Method for preparing silanol by utilizing photocatalytic oxidation of silane | |
| CN102600820A (en) | Process for producing titanium-containing silicon oxide catalyst, the catalyst, and process for producing olefin compound with the catalyst | |
| CN104437636B (en) | Titaniferous porous silica Si catalyst, preparation method and its usage | |
| CN105367518B (en) | The method of coproduction epoxides and cumyl peroxide | |
| CN101115561A (en) | Method for manufacturing titanium-containing silicon oxide catalyst and catalyst | |
| TW568797B (en) | Method for producing titanium-containing silicon oxide catalyst and catalyst prepared thereby | |
| CN102295533B (en) | Preparation method of alpha, alpha-dimethyl benzyl alcohol | |
| CN105315237A (en) | Synthetic method of 3,4-epoxy-1-butylene | |
| CN105272945A (en) | Production method for epichlorohydrin | |
| CN1120831C (en) | Technological process of alkali anion exchange resin catalyzed synthesis of butanolone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |