CN101544620A - Preparation method of epoxy cyclohexane - Google Patents
Preparation method of epoxy cyclohexane Download PDFInfo
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- CN101544620A CN101544620A CN200810102836A CN200810102836A CN101544620A CN 101544620 A CN101544620 A CN 101544620A CN 200810102836 A CN200810102836 A CN 200810102836A CN 200810102836 A CN200810102836 A CN 200810102836A CN 101544620 A CN101544620 A CN 101544620A
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Abstract
The invention discloses a preparation method of epoxy cyclohexane, which is characterized in that under the conditions that the temperature is 0-180 DEG C and the pressure is 0.1-3.0 MPa, cyclohexene, oxygen, hydrogen, diluent gas, solvent and catalyst are mixed, contacted and reacted, wherein the mol ratio of the cyclohexene, the oxygen, the hydrogen and the diluent gas is 1: (0.1-10) : (0.1-10) : (0-100), the mass ratio of the cyclohexene and the catalyst is (0.5-50) : 1, and the mass ratio of the solvent and the catalyst is (0-1000) : 1; the catalyst is a micropore titanium silicon material or a composition containing the micropore titanium silicon material, the component of the micropore titanium silicon material is expressed by an oxide form as xTiO2.100SiO2.yEmOn.zE, wherein the value of x is 0.001-50.0, the value of (y+z) is 0.005-20.0, and y/z is less than 5; E is one or more selected from noble metals of Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and Au, and m and n are numbers which satisfy the requirements of E oxidation state; and the material crystal grains contain hollow or concave-convex structures.
Description
Technical field
The invention relates to a kind of method of catalyzed oxidation tetrahydrobenzene, further say so about being the method for catalyst cyclohexene oxide with a kind of titanium silicalite material that contains precious metal.
Background technology
Epoxy cyclohexane is a kind of important fine chemical material and intermediate, can be as the reactive thinner of Resins, epoxy, can also also be the raw material of organic compound such as synthesizing new higher effective and lower toxic pesticide propargite and cyclohexanediol, cyclohexadiene as the raw material of synthetic dicyclohexyl-18-hat-6, thricyclohexyl three azepines-crown compounds such as 18-hat-6.Simultaneously, the more active chemical property of epoxy cyclohexane makes it have good application prospects in efficiency light curing field.Along with continually developing of purposes, the demand of epoxy cyclohexane also grows with each passing day.
At present, the domestic full scale plant that does not also have independent epoxy cyclohexane to produce, it mainly is to obtain by a small amount of epoxy cyclohexane that reclaims by-product in the cyclohexane oxidation technological process.Adopt adding methyl alcohol or ethanol to make it to distill the method that obtains product as having disclosed among the CN1106784A with epoxy cyclohexane formation azeotrope.This method is by the recycling process, the flow process complexity.
The as easy as rolling off a log hydrolysis of epoxy cyclohexane, therefore traditional acid system excessively that is used for synthesizing epoxy compound can not be applicable to its production, and self costs an arm and a leg peracid, has potential safety hazard simultaneously, has been difficult to industrial value.The yield of chlorohydrination synthesis epoxy cyclohexane is low, and simultaneously just there are a lot of problem demanding prompt solutions in chlorohydrination itself, as equipment corrosion, seriously polluted etc.
Adopt reaction control phase transfer catalyst to carry out catalysis epoxidation among the CN1161346C and prepare epoxy cyclohexane, but owing to make oxygen source with hydrogen peroxide or alkyl peroxide, price is expensive, and the reaction system complexity, is unfavorable for industrial production.
CN 1542007 A reoxidize the method for tetrahydrobenzene after having reported and having utilized molecular oxygen as oxidant that aldehyde etc. is oxidized to peroxy acid, have corrosion dangerous but consume the acid that aldehyde produces to equipment, the purification that also is unfavorable for product with separate and catalyst system complexity.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who is different from the epoxy cyclohexane of prior art.
The preparation method of epoxy cyclohexane provided by the invention, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with tetrahydrobenzene, oxygen, hydrogen, diluent gas, solvent and catalyst mix contact reacts, tetrahydrobenzene and oxygen, hydrogen, the mol ratio of diluent gas is 1:(0.1～10): (0.1～10): (0～100), the mass ratio of tetrahydrobenzene and catalyzer is (0.5-50): 1, the mass ratio of solvent and catalyzer is (0～1000): 1, said catalyzer is a kind of micropore titanium-silicon material or the composition that contains this micropore titanium-silicon material, and the composition of micropore titanium-silicon material is expressed as xTiO with the form of oxide compound
2100SiO
2YE
mO
nZE, wherein the x value is 0.001～50.0, (y+z) value is 0.005～20 and y/z＜1, E represents to be selected from one or more precious metals among Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and the Au, and m and n satisfy the required number of E oxidation state, and this material grains contains promising hollow or convex-concave structure.
Among the preparation method of epoxy cyclohexane provided by the invention, said micropore titanium-silicon material discloses in application number is 200710064981.6 Chinese patent application, in the representation of oxide compound, the preferred 0.005-25 of x value, (y+z) be worth preferred 0.01-10, the preferred Pd of precious metal E, among Pt and the Au one or more, more preferably Pd and/or Pt, when precious metal is two or more, the value of said y be every kind of precious metal y value and, the value of said z be every kind of precious metal z value and, for example, when selected precious metal was Pt and Pd, the composition of this material was expressed as xTiO with the form of oxide compound
2100SiO
2Y
1PtOy
2PdOz
1Ptz
2Pd, i.e. y=y
1+ y
2, z=z
1+ z
2The crystal grain of this material contains hollow or concavo-convex structure, and the radical length of the cavity part of hollow crystal grain is 2～300 nanometers, is preferably 10～200 nanometers; This material is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 50 milligrams/gram, is preferably at least 70 milligrams/gram; There is hysteresis loop between the adsorption isothermal line of its cryogenic nitrogen absorption and the desorption isotherm; The shape of cavity part is not changeless, can be different shapes such as rectangle, circle, irregular cycle, irregular polygon, or one or more the combination in these shapes; Its crystal grain can be single crystal grain or the gathering crystal grain that is gathered into by a plurality of crystal grain.
Said micropore titanium-silicon material, crystal grain comprise hollow or concavo-convex structure, help the diffusion of reactant and product molecule, and the synergy of precious metal and HTS is improved, and have overcome precious metal accumulative drawback.
In being 200710064981.6 Chinese patent application, application number discloses two kinds of preparation methods of above-mentioned said micropore titanium-silicon material simultaneously.
One of method is HTS, protective material, noble metal source and reductive agent to be joined to change hydrothermal treatment consists in the reactor in the solution that contains alkali source behind the mixing over to earlier, filters, washs, is drying to obtain, and more particularly comprises:
(1) earlier HTS, protective material, noble metal source and reductive agent are joined mixing in the solution that contains alkali source, it consists of HTS (gram): protective material (mole): alkali source (mole): reductive agent (mole): noble metal source (gram is in precious metal simple substance): water (mole)=100:(0.0001-5.0): (0.005-5.0): (0.005-15.0): (0.005-10.0): (200-10000);
(2) mixture of step (1) gained is changed in the reactor under the hydrothermal treatment consists condition, react again, and reclaim product and promptly get micropore titanium-silicon material of the present invention.
Wherein, form in the step (1) and be preferably HTS (gram): protective material (mole): alkali source (mole): reductive agent (mole): noble metal source (gram is in precious metal simple substance): water (mole)=100:(0.005-1.0): (0.01-2.0): (0.01-10.0): (0.01-5.0): (500-5000).
Said HTS comprises the HTS of all kinds structure in the step (1), as TS-1, and TS-2, Ti-BETA, Ti-MCM-22 etc. are preferably TS-1.
The said protective material of step (1) is meant polymkeric substance or tensio-active agent; wherein polymkeric substance can be polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, polyethylene etc. and derivative thereof, and tensio-active agent can be anion surfactant, cats product and nonionogenic tenside.
The said reductive agent of step (1) can be hydrazine, hydroborate, Trisodium Citrate etc., and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazonium sulfate etc., and hydroborate can be sodium borohydride, POTASSIUM BOROHYDRIDE etc.
The said noble metal source of step (1) is selected from the inorganics or the organism of above-mentioned precious metal, can be other complex compound of oxide compound, halogenide, carbonate, nitrate, ammonium salt, ammonia chloride salt, oxyhydroxide or precious metal etc.With the palladium is example, and the palladium source can be inorganic palladium source and/or organic palladium source.Wherein inorganic palladium source can be other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.
The said alkali source of step (1) is inorganic alkali source or organic alkali source.Wherein inorganic alkali source is ammoniacal liquor, sodium hydroxide, potassium hydroxide, hydrated barta etc.; Organic alkali source is urea, quaternary amine alkali compounds, fat amine compound, alcamine compound or the mixture be made up of them.
Said its general formula of quaternary ammonium hydroxide compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1-4 carbon atom, preferably propyl group.
Its general formula of said fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene group, n=1 or 2 with 1-6 carbon atom; Said fat amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
Its general formula of said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3; Said alcamine compound is monoethanolamine, diethanolamine or trolamine.
The said hydrothermal treatment consists condition of step (2) is under temperature 80-200 ℃ and autogenous pressure hydrothermal treatment consists 2-360 hour, the process of said recovery product is well known to those skilled in the art, there is no special feature, generally include processes such as crystallization product washing, dryings.
Two of method comprises the steps:
(1) titanium source, silicon source, alkali source, protective material, noble metal source and water are mixed the back in 120～200 ℃ of hydrothermal crystallizings 6 hours～10 days; after drying is filtered in taking-up, roasting gets middle crystalline material; the mole of mixture consists of the silicon source: titanium source: alkali source: noble metal source: protective material: water=100:(0.005-50.0): (0.005-20.0): (0.005-10.0): (0.005-5.0): (200-10000), wherein the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, noble metal source is in simple substance;
(2) the middle crystalline material with step (1) gained changes in the last filtrate of step (1), after the mol ratio of the noble metal source that is added in adding and the step (1) is the reductive agent of 0.1-10, in reactor under temperature 80-200 ℃ and autogenous pressure hydrothermal treatment consists 2-360 hour, and reclaim product and promptly get micropore titanium-silicon material of the present invention.
Wherein, the mole of step (1) mixture is formed the silicon source that is preferably: titanium source: alkali source: noble metal source: protective material: water=100:(0.01-10.0): (0.01-10.0): (0.01-5.0): (0.01-1.0): (500-5000).
The said silicon of step (1) source is silica gel, silicon sol or organosilicon acid esters, preferably organosilicon acid esters; Said its general formula of organosilicon acid esters is R
4 4SiO
4, R wherein
4Preferably have the alkyl of 1-4 carbon atom, be more preferably ethyl.
The said titanium of step (1) source is inorganic titanium salt or organic titanate, preferably organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
5)
4, R wherein
5For having the alkyl of 1-6 carbon atom, more preferably has the alkyl of 2-4 carbon atom.
Said alkali source is the mixture that quaternary amine alkali compounds or quaternary amine alkali compounds and fat amine compound, alcamine compound are formed in the step (1).Wherein, said its general formula of quaternary ammonium hydroxide compounds is (R
6)
4NOH, R
6For having the alkyl of 1-4 carbon atom, preferably propyl group.Its general formula of said fat amine compound is R
7(NH
2)
n, R wherein
7Be selected from alkyl or alkylidene group, n=1 or 2, for example ethamine, n-Butyl Amine 99, butanediamine, hexanediamine etc. with 1-4 carbon atom.Its general formula of said alcamine compound is (HOR
8)
mNH
(3-m)R wherein
8Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3, for example monoethanolamine, diethanolamine, trolamine etc.
The said protective material of step (1) is meant polymkeric substance or tensio-active agent; wherein polymkeric substance can be polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, polyethylene etc., and tensio-active agent can be anion surfactant, cats product and nonionogenic tenside.
The said noble metal source of step (1) is selected from the organism or the inorganics of precious metal, can be other complex compound etc. of their oxide compound, halogenide, carbonate, nitrate, ammonium salt, chlorination ammonium salt, oxyhydroxide or precious metal.With the palladium source is example, can be inorganic palladium source and/or organic palladium source, wherein inorganic palladium source can be other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.
Said reductive agent can be azanol, hydrazine, hydroborate, Trisodium Citrate etc. in the step (1), and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazonium sulfate etc., and hydroborate can be sodium borohydride, POTASSIUM BOROHYDRIDE etc.
The preparation method of epoxy cyclohexane provided by the invention can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, behind tetrahydrobenzene, solvent, catalyzer adding reactor, add oxygen, hydrogen, diluent gas continuously; And continuous mode can adopt fixed-bed reactor when carrying out, and behind the catalyzer of packing into solvent, tetrahydrobenzene, oxygen, hydrogen, diluent gas is added continuously; Also can adopt slurry bed reactor, catalyzer, tetrahydrobenzene, solvent making beating back are added oxygen, hydrogen, diluent gas continuously, the while is separated product constantly.Adopting under periodical operation or the operate continuously mode, reacting total gas space velocity is 10～10000h
-1, be preferably 100～5000h
-1
Method provided by the invention can also adopt closed still reaction, and soon catalyzer, solvent, tetrahydrobenzene and oxygen, hydrogen, diluent gas add simultaneously and mix afterreaction in the still.
In the method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of tetrahydrobenzene and oxygen is preferably 1:(0.2～5), the mol ratio of tetrahydrobenzene and hydrogen is preferably 1:(0.2～5), the mass ratio of solvent and catalyzer is preferably (10～500): 1.
In the method provided by the invention, temperature of reaction is preferably 20～120 ℃, and reaction pressure is preferably 0.3～2.5MPa.
In the method provided by the invention, diluent gas and solvent can be added, also diluent gas or solvent can be do not added according to practical situation.
Said diluent gas can be rare gas elementes such as nitrogen, argon gas, helium, neon, also can be carbonic acid gas, methane, ethane, propane etc.
Said solvent is selected from one or more the mixture in water, alcohol, ketone and the nitrile, and said alcohol is nitriles such as ketones such as alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone, butanone or acetonitrile.In said solvent, the mixture of one or more in methyl alcohol, the trimethyl carbinol and the water more preferably.
In the method provided by the invention, catalyzer is micropore titanium-silicon material or the composition that contains micropore titanium-silicon material, and wherein said composition is selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by micropore titanium-silicon material and other and forms.
The preparation method of epoxy cyclohexane provided by the invention, in the presence of hydrogen, with molecular oxygen as oxidant, need not to add any inhibitor or initiator in the unstripped gas, employing contains precious metal, especially contains the hollow micropore titanium-silicon material of palladium as catalytic active component, increased the velocity of diffusion of reactant and product, reduced the generation of side reactions such as open loop, over oxidation, raw material tetrahydrobenzene transformation efficiency height, good product selectivity, activity stability are good.
Description of drawings
Fig. 1 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 1 sample A.
Fig. 2 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 2 sample B.
Fig. 3 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 3 sample C.
Fig. 4 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 4 sample D.
Fig. 5 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 5 sample E.
Fig. 6 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 6 sample F.
Fig. 7 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 7 sample G.
Fig. 8 is the adsorption-desorption isothermal curve figure of the low temperature nitrogen absorption of embodiment 8 sample H.
Fig. 9 is transmission electron microscope (TEM) photo of embodiment 1 sample A.
Figure 10 is transmission electron microscope (TEM) photo of embodiment 2 sample B.
Figure 11 is transmission electron microscope (TEM) photo of embodiment 3 sample C.
Figure 12 is transmission electron microscope (TEM) photo of embodiment 4 sample D.
Figure 13 is transmission electron microscope (TEM) photo of embodiment 5 sample E.
Figure 14 is transmission electron microscope (TEM) photo of embodiment 6 sample F.
Figure 15 is transmission electron microscope (TEM) photo of embodiment 7 sample G.
Figure 16 is transmission electron microscope (TEM) photo of embodiment 8 sample H.
Embodiment
Following embodiment and Comparative Examples will be further described the present invention, but therefore not limit content of the present invention.
Among Comparative Examples and the embodiment, used reagent is commercially available chemically pure reagent.
Used HTS is by prior art Zeolites among Comparative Examples and the embodiment, 1992, and the TS-1 sieve sample of the method preparation described in the 943rd～950 page of the Vol.12.
The adsorption-desorption isothermal curve of the low temperature nitrogen absorption of sample is to measure according to ASTM D4222-98 standard method on the static n2 absorption apparatus of the ASAP2405 of U.S. Micromeritics company.
The transmission electron microscope photo (TEM) of sample is at the Dutch Tecnai G of FEI Co.
2Obtain acceleration voltage 20kV on the F20S-TWIN type transmission electron microscope.
In Comparative Examples: the comparative catalyst need be in nitrogen hydrogen mixed gas atmosphere before reacting, temperature is reduction activation 3 hours under 300 ℃ the condition.
The preparation process of micropore titanium-silicon material A, the B that uses in embodiment 1～8 explanation method provided by the invention, C, D, E, F, G, H.
Embodiment 1
Get in the aqueous solution (mass percent concentration 10%) that nitric acid ammonia palladium complex solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in the palladium atom) and an amount of hydrazine hydrate and cetyl trimethylammonium bromide join TPAOH and mix, HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia palladium complex (gram is in palladium): water (mole)=100:0.005:0.5:3.0:2.0:1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 150 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and under 180 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material A that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 4TiO
2100SiO
20.01PdO0.09Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 1), the transmission electron microscope photo demonstrates it and is hollow structure (Fig. 9).
Embodiment 2
Get in the aqueous solution (mass percent concentration 15%) that palladium chloride solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in the palladium atom) and appropriate hydrochloric acid hydrazine and polypropylene join sodium hydroxide and mix, HTS (gram) wherein: polypropylene (mole): sodium hydroxide (mole): hydrazine hydrochloride (mole): palladous oxide (gram is in palladium): water (mole)=100:0.9:1.8:0.15:0.1:4600.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 24 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and under 110 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material B that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 8TiO
2100SiO
20.006PdO0.008Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 2), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 10).
Embodiment 3
With positive tetraethyl orthosilicate, tetrabutyl titanate, concentration is to mix in the acid chloride solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration is 10%) that tween 80 joins TPAOH and butanediamine; wherein mole is formed the silicon source: titanium source: TPAOH: butanediamine: palladium source: protective material: water=100:0.03:0.5:0.1:0.05:0.02:550, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrate, added behind an amount of hydrazine hydrate under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material C that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 0.008TiO
2100SiO
20.01PdO0.2Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 3), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 11).
Embodiment 4
With positive tetraethyl orthosilicate, tetrabutyl titanate, concentration is to mix in the ammonia chloride palladium solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that Sodium dodecylbenzene sulfonate joins TPAOH; add under the high degree of agitation in batches; continue to stir for some time; wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:2.0:5.2:2.0:0.5:2500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 150 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrate, added behind the appropriate hydrochloric acid hydrazine under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours, gains are filtered, wash with water, after the seasoning, and under 120 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material D that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 19TiO
2100SiO
20.5PdO1.3Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 4), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 12).
Embodiment 5
Get in the aqueous solution (mass percent concentration 10%) that acid chloride solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in the palladium atom) and right amount of boron sodium hydride and tween 80 join butanediamine and mix, HTS (gram) wherein: tween 80 (mole): butanediamine (mole): sodium borohydride (mole): acid chloride (gram is in palladium): water (mole)=100:0.1:0.02:0.05:0.03:520.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material E that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 0.1TiO
2100SiO
20.1PdO0.75Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 5), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 13).
Embodiment 6
Get in the aqueous solution (mass percent concentration 10%) that ammonia chloride palladium solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in the palladium atom) and an amount of hydrazonium sulfate and Sodium dodecylbenzene sulfonate join TPAOH and mix, add under the high degree of agitation in batches, continue to stir for some time, HTS (gram) wherein: Sodium dodecylbenzene sulfonate (mole): TPAOH (mole): hydrazonium sulfate (mole): ammonia chloride palladium (gram is in palladium): water (mole)=100:0.5:0.1:8.5:4.8:2000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 240 hours under 90 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and under 120 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material F that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 0.04TiO
2100SiO
20.6PdO5.1Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 6), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 14).
Embodiment 7
With positive tetraethyl orthosilicate, tetraethyl titanate, concentration is that the acid chloride solution of 0.01g/mL (in the palladium atom) and cetyl trimethylammonium bromide join in the TPAOH (mass percent concentration 13%) and mix; silicon source wherein: titanium source: alkali source: palladium source: protective material: water=100:8.2:7.5:0.1:0.05:800, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrate, added behind the appropriate hydrochloric acid hydrazine under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material G that contains precious metal of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 23TiO
2100SiO
20.04PdO0.8Pd the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 7), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 15).
Embodiment 8
Get in the aqueous solution (mass percent concentration 14%) that nitric acid ammonia palladium that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in the palladium atom) and nitric acid ammonia platinum complex solution and hydrazine hydrate and cetyl trimethylammonium bromide join TPAOH and mix, HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia platinum (gram, in platinum): nitric acid ammonia palladium (gram is in palladium): water (mole)=100:0.1:1.2:2.0:0.8:1.2:1800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 180 ℃ temperature and autogenous pressure, and gains are filtered, wash with water, after the seasoning, and under 180 ℃, continued dry 3 hours, promptly get the novel micropore titanium-silicon material H that contains two precious metals of the present invention.Through characterizing, its form of forming with oxide compound can be expressed as 4TiO
2100SiO
20.3PdO0.9Pd0.1PtO0.7Pt the adsorption-desorption isothermal curve figure of its low temperature nitrogen absorption has hysteresis loop (Fig. 8), the transmission electron microscope photo demonstrates it and is hollow structure (Figure 16).
Comparative Examples 1,2 explanation load type palladium/HTS comparative catalysts' preparation process.
Comparative Examples 1
Get titanium-silicon molecular sieve TS-1 sample 10 grams and 15mL water and join the PdCl that 5mL concentration is 0.01g/mL
2In the aqueous solution, be 40 ℃ in temperature and stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature is 48 hours then, promptly obtains load type palladium/HTS (0.5%Pd/TS-1) catalyzer.
Comparative Examples 2
Get titanium-silicon molecular sieve TS-1 sample 10 grams and join the PdCl that 20mL concentration is 0.01g/mL
2In the aqueous solution, be 40 ℃ in temperature and stirred 24 hours down, suitably sealing therebetween, natural drying at room temperature is 48 hours then, promptly obtains load type palladium/HTS (2%Pd/TS-1) catalyzer.
Embodiment 9-18 explanation is the preparation process that catalyzer carries out epoxy cyclohexane with the micropore titanium-silicon material A-H of embodiment 1-8 preparation.
Embodiment 9
With tetrahydrobenzene, oxygen (4% volume, all the other are nitrogen), hydrogen, solvent and A be 1:1:1 according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, the mass ratio of solvent tertiary butanol and catalyzer is 200, is that 60 ℃ of pressure are 0.5MPa in temperature, is 1000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 13%; The epoxy cyclohexane selectivity is 94%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 11%; The epoxy cyclohexane selectivity is 92%.
Embodiment 10
With tetrahydrobenzene, oxygen, hydrogen (10% volume, all the other are argon gas), solvent and B be 1:2:1 according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 20, is that 30 ℃ of pressure are under the 1.5MPa in temperature, is 150h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 11%; The epoxy cyclohexane selectivity is 93%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 10%; The epoxy cyclohexane selectivity is 90%.
Embodiment 11
With tetrahydrobenzene, oxygen (80% volume, all the other are carbonic acid gas), hydrogen, solvent and C be 1:5:2 according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, the mass ratio of solvent tertiary butanol and catalyzer is 80, is that 40 ℃ of pressure are under the 0.8MPa in temperature, is 2000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 12%; The epoxy cyclohexane selectivity is 92%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 11%; The epoxy cyclohexane selectivity is 91%.
Embodiment 12
With tetrahydrobenzene, oxygen, hydrogen (4% volume, all the other are methane), solvent and D be 1:2:5 according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 400, is that 50 ℃ of pressure are under the 0.5MPa in temperature, is 4000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 10%; The epoxy cyclohexane selectivity is 94%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 9%; The epoxy cyclohexane selectivity is 92%.
Embodiment 13
Is 1:0.5:3 with tetrahydrobenzene, oxygen, hydrogen, solvent and E according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, and the mass ratio of aqueous solvent and catalyzer is 100, is that 80 ℃ of pressure are under the 2.5MPa in temperature, is 3000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 9%; The epoxy cyclohexane selectivity is 93%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 7%; The epoxy cyclohexane selectivity is 92%.
Embodiment 14
Is 1:3:0.5 with tetrahydrobenzene, oxygen, hydrogen, solvent and F according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 300, is that 30 ℃ of pressure are under the 1.2MPa in temperature, is 1500h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 12%; The epoxy cyclohexane selectivity is 94%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 10%; The epoxy cyclohexane selectivity is 91%.
Embodiment 15
Present embodiment is to utilize the G of embodiment 7 preparations to do the reaction that catalyzer carries out catalysis cyclohexene oxide under the hydrogen and oxygen existence, specific as follows: is 1:2:1 with tetrahydrobenzene, oxygen, hydrogen, solvent and G according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, the mass ratio of solvent methanol and catalyzer is 20, in temperature is that 70 ℃ of pressure are under the 1.5MPa, is 600h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 11%; The epoxy cyclohexane selectivity is 93%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 10%; The epoxy cyclohexane selectivity is 90%.
Embodiment 16
Is 1:2:2 with tetrahydrobenzene, oxygen, hydrogen, solvent and H according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 50, is that 40 ℃ of pressure are under the 0.5MPa in temperature, is 2000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 14%; The epoxy cyclohexane selectivity is 93%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 12%; The epoxy cyclohexane selectivity is 92%.
Embodiment 17
The present embodiment explanation utilizes the A of embodiment 1 preparation to do catalyzer carries out the cyclohexene oxide reaction in the tank reactor of sealing process.
Is 1:5:1:1 with tetrahydrobenzene, oxygen, hydrogen, solvent tertiary butanol and A according to the mol ratio of tetrahydrobenzene and the trimethyl carbinol, oxygen, hydrogen, and the mass ratio of solvent tertiary butanol and catalyzer is 50, is that 60 ℃ of pressure are to react under the 0.8MPa in temperature.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 13%; The epoxy cyclohexane selectivity is 95%.
The result who reacts 8 hours is as follows: the tetrahydrobenzene transformation efficiency is 25%; The epoxy cyclohexane selectivity is 91%.
Embodiment 18
The present embodiment explanation utilizes the B of embodiment 2 preparations to do catalyzer carries out the cyclohexene oxide reaction in the tank reactor of sealing process.
Is 1:20:2:2 with tetrahydrobenzene, oxygen, hydrogen, solvent methanol and B according to the mol ratio of tetrahydrobenzene and methyl alcohol, oxygen, hydrogen, and the mass ratio of methyl alcohol and catalyzer is 200, is that 30 ℃ of pressure are to react under the 1.8MPa in temperature.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 15%; The epoxy cyclohexane selectivity is 96%.
The result who reacts 8 hours is as follows: the tetrahydrobenzene transformation efficiency is 32%; The epoxy cyclohexane selectivity is 90%.
Condition and result that Comparative Examples 3,4 explanations utilize the comparative catalyst of Comparative Examples 1,2 preparations to carry out the reaction of catalyzed oxidation tetrahydrobenzene.
Comparative Examples 3
Load type palladium/HTS (0.5%Pd/TS-1) that the explanation of this Comparative Examples utilizes Comparative Examples 1 to prepare is made catalyzer and is carried out the process that the catalyzed oxidation tetrahydrobenzene prepares epoxy cyclohexane.
Is 1:1:1 with tetrahydrobenzene, oxygen, hydrogen, solvent and catalyzer according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, and the mass ratio of solvent tertiary butanol and catalyzer is 200, is that 60 ℃ of pressure are under the 0.5MPa in temperature, is 1000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 5%; The epoxy cyclohexane selectivity is 91%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 3%; The epoxy cyclohexane selectivity is 85%.
Comparative Examples 4
Load type palladium/HTS (2%Pd/TS-1) that the explanation of this Comparative Examples utilizes Comparative Examples 2 to prepare is made catalyzer and is carried out the process that the catalyzed oxidation tetrahydrobenzene prepares epoxy cyclohexane.
Is 1:1:1 with tetrahydrobenzene, oxygen, hydrogen, solvent and catalyzer according to the mol ratio of tetrahydrobenzene and oxygen, hydrogen, and the mass ratio of solvent methanol and catalyzer is 200, is that 60 ℃ of pressure are under the 0.5MPa in temperature, is 1000h in total gas volume air speed
-1Under react.
The result who reacts 2 hours is as follows: the tetrahydrobenzene transformation efficiency is 6%; The epoxy cyclohexane selectivity is 90%.
The result who reacts 20 hours is as follows: the tetrahydrobenzene transformation efficiency is 2%; The epoxy cyclohexane selectivity is 83%.
From the reaction result of embodiment 9-18 and Comparative Examples 3,4 as can be seen: method tetrahydrobenzene transformation efficiency of the present invention is higher, product epoxy cyclohexane selectivity is better, and has good activity stability.
Claims (10)
1. the preparation method of an epoxy cyclohexane, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with tetrahydrobenzene, oxygen, hydrogen, diluent gas, solvent and catalyst mix contact reacts, tetrahydrobenzene and oxygen, hydrogen, the mol ratio of diluent gas is 1:(0.1～10): (0.1～10): (0～100), the mass ratio of tetrahydrobenzene and catalyzer is (0.5-50): 1, the mass ratio of solvent and catalyzer is (0～1000): 1, said catalyzer is a kind of micropore titanium-silicon material or the composition that contains this micropore titanium-silicon material, and the composition of micropore titanium-silicon material is expressed as xTiO with the form of oxide compound
2100SiO
2YE
mO
nZE, wherein the x value is 0.001～50.0, (y+z) value is 0.005～20.0 and y/z＜1, E represents to be selected from one or more precious metals among Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and the Au, and m and n satisfy the required number of E oxidation state, and this material grains contains hollow or concaveconvex structure.
2. according to the method for claim 1, it is characterized in that said precious metal E is Pt and/or Pd.
3. according to the method for claim 1, it is characterized in that said x value is 0.005～25.0, (y+z) value is 0.01～10.0.
4. according to the method for claim 1, it is characterized in that the said composition that contains micropore titanium-silicon material is selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by micropore titanium-silicon material and other and forms.
5. according to the method for claim 1, it is characterized in that said diluent gas is selected from nitrogen, argon gas, helium, neon, perhaps is selected from carbonic acid gas, methane, ethane, propane.
6. according to the method for claim 1, the mol ratio that it is characterized in that said tetrahydrobenzene and oxygen is 1:(0.2～5.0), the mol ratio of tetrahydrobenzene and hydrogen is 1:(0.2～5.0), the mass ratio of solvent and catalyzer is (10～500): 1.
7. according to the method for claim 1, it is characterized in that temperature of reaction is 20～120 ℃, reaction pressure is 0.3～2.5MPa.
8. according to the method for claim 1, it is characterized in that said solvent is selected from one or more the mixture in water, alcohol, ketone and the nitrile.
9. according to the method for claim 1, it is characterized in that said solvent is selected from one or more the mixture in methyl alcohol, the trimethyl carbinol and the water.
10. according to the method for claim 1, it is characterized in that adopting periodical operation or operate continuously mode, reacting total gas space velocity is 10～10000h
-1
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