CN101397235B - Method for catalytic oxidation of cyclohexane - Google Patents
Method for catalytic oxidation of cyclohexane Download PDFInfo
- Publication number
- CN101397235B CN101397235B CN200710175280XA CN200710175280A CN101397235B CN 101397235 B CN101397235 B CN 101397235B CN 200710175280X A CN200710175280X A CN 200710175280XA CN 200710175280 A CN200710175280 A CN 200710175280A CN 101397235 B CN101397235 B CN 101397235B
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- hexanaphthene
- solvent
- catalyzer
- oxygen
- 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.)
- Active
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for catalytic oxidation of cyclohexane, which is characterized in that the cyclohexane, oxygen, hydrogen, dilution gas, a solvent and a catalyst are mixed, contacted and reacted under the conditions of the temperature of 0 to 180 DEG C and the pressure of 0.1 to 3.0MPa, the molar ratio of the cyclohexane to the oxygen, the hydrogen and the dilution gas is 1: (0.1 to 10): (0.1 to 10): (0 to 100), the weight ratio of the cyclohexane to the catalyst is (0.5 to 50): 1, the weight ratio of the solvent to the catalyst is (0 to 1000): 1, the catalyst is a microporoustitanium silicon material or a composition containing the microporous titanium silicon material, the composition of the microporous titanium silicon material can be represented as follows by using the form of oxides: xTiO2 question mark 100SiO2 question mark yEmOn question mark Ze, wherein, the value of x is 0.001 to 50.0, the value of (y plus z) is 0.005 to 20.0 and y/z is less than 1, E refers to one or a plurality of precious metals selected from Ru, Rh, Pd, Re, Os, Ir, Pt and Au, m and n are numbers which are required by oxidation state of E, and the grain part or all of the material is a hollow structure. The method has higher effective utilization rate of the hydrogen.
Description
Technical field
The invention relates to a kind of method of catalyzed oxidation hexanaphthene, further say so about being the method for catalyst oxidizing ethyle alkyl with a kind of titanium silicalite material that contains precious metal.
Background technology
Pimelinketone is a kind of important chemical material, is widely used in fiber, viton, industrial coating, medicine, agricultural chemicals, the organic solvent industry.Particularly because the developing rapidly of polymeric amide industry, as demand every year of the pimelinketone of preparation nylon 6 and nylon 66 midbodys all more than 1,000,000 tons.Now; The cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and benzene partial hydrogenation method; And wherein cyclohexane oxidation process is that the main process of producing pimelinketone is gone up in industry, accounts for more than 90%, still; It is minimum that cyclohexane oxidation process also is considered to efficient, is one of key and bottleneck of restriction caprolactam production.Utilize cyclohexane oxidation to produce pimelinketone in the industry three kinds of methods are generally arranged: a kind of is that the employing cobalt salt is the catalyzed oxidation of catalyzer, and this method cyclohexane conversion is higher, but the reaction kettle easy scale formation is eliminated basically owing to formation hexanodioic acid cobalt makes at present; The 2nd, boric acid class catalytic oxidation, this method initial cost is high, and energy consumption is high, and technology is very complicated, and operation easier is big, and is easy to cause equipment and pipeline seriously to stop up; The 3rd, with the non-catalyst oxidation method of air direct oxidation, this method has effectively been avoided the problem of reactor fouling, in industry, widely applies; But this method is complicated, and intermediate steps is many, and cyclohexane conversion is low; The hexanaphthene internal circulating load is big, and energy consumption is high, pollutes also bigger; Particularly in the cyclohexyl hydroperoxide decomposition course, pimelinketone, hexalin selectivity are relatively poor, and yield is low.In addition, a large amount of spent lye treatment difficulties that cyclohexane oxidation process produces are still a global environmental protection difficult problem so far.
Therefore, a kind of cyclohexane conversion is high, and pimelinketone and hexalin selectivity are good, and the method for particularly polluting little, environmentally friendly and simple new catalyzed oxidation hexanaphthene is of great practical significance.Last century early eighties, Italian Taramasso discloses a kind of new catalytic material-HTS in USP4410501; It to hydrocarbon, alcohol, phenol etc. have good selective oxidation (EP0230949, USP4480135, USP4396783); Catalyzer with other type is compared, and adopt the TS-1 molecular sieve as the system that catalyzer carries out oxidation following remarkable advantage to be arranged: (1) reaction conditions is gentle, can under normal pressure, low temperature (20-100 ℃), carry out; (2) oxidation purpose product yield is high; Selectivity is good, and (3) process is simple, environmental friendliness.This molecular sieve has been applied to the oxidation of phenol preparing benzenediol and has realized industriallization.
Spinace etc. (J.Catal, 1995,157:631-635) the titanium molecular sieve catalysis oxidizing ethyle alkyl has been carried out a series of research.From research, draw: hexanaphthene initial oxidation on TS-1 is a hexalin, reoxidizes to be pimelinketone.Because of selecting optionally reason of type, hexalin will be oxidized to pimelinketone further in the TS-1 zeolite cages, then be oxidized to multiple oxide compound at the TS-1 outside surface.After adding 2,6 di tert butyl 4 methyl phenol, can suppress the non-selective oxidation of catalyzer outside surface effectively, improve the selectivity of product pimelinketone.
Tao Jialin etc. (J.Na tural Gas Chem.2001,10:295-307) and U1fSchuchardt etc. (Applied Catal.A:Gen.2001 211:1-17) also studies the titanium molecular sieve catalysis oxidizing ethyle alkyl.This method reaction conditions is gentle, target product yield is high, and have that technological process is simple, plant investment is few, energy-saving and cost-reducing, the three wastes are few, characteristics such as environmentally friendly.But still the problem that the ubiquity cyclohexane conversion is low, the hydrogen peroxide utilization ratio is low, and because H
2O
2Extremely unstable, meet heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, in packing, storage, transportation, will take special security measures.Receive the limitation of cost and safety-problems, and preparation H
2O
2Need the independent equipment and the recycle system, expensive bigger, the situ production expense is very high, and needs the technology of exploitation and reacting phase coupling.Before not having stricter environmental regulation appearance, this TS-1/H
2O
2The system industriallization has the certain economic obstacle.
Molecular oxygen is cheap and easy to get and pollution-free, is optimal oxygen source.Utilize H
2And O
2Directly synthetic H
2O
2, can reduce TS-1/H greatly
2O
2System industriallization cost.Pt, Pd are H
2And O
2Synthetic H
2O
2Active principle, have bibliographical information that it is loaded on the titanium silicalite material original position and generate H
2O
2Be used for the research of propylene gas-phase epoxidation reaction.As, Meiers R. etc. (J.Catal., 1998, be that catalyzer is studied PROPENE IN GAS PHASE OXIDATION with Pt-Pd/TS-1 176:376-386).Do not see report so far at aspects such as catalyzed oxidation hexanaphthenes.
Summary of the invention
The purpose of this invention is to provide a kind of micropore titanium-silicon material with uniqueness is the novel method of catalyst oxidizing ethyle alkyl.
The method of catalyzed oxidation hexanaphthene 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 hexanaphthene, oxygen, hydrogen, diluents, solvent and catalyst mix contact reacts; The mol ratio of hexanaphthene and oxygen, hydrogen, diluents is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of hexanaphthene and catalyzer are (0.5-50): 1, and the mass ratio of solvent and catalyzer is (0～1000): 1; Said catalyzer is a kind of micropore titanium-silicon material or the compsn 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 representes to be selected from one or more precious metals among Ru, Rh, Pd, Re, Os, Ir, Pt and the Au, and m and n satisfy the required number of E oxidation state, and this material grains partly or entirely is a hollow structure.
In the method for catalyzed oxidation hexanaphthene provided by the invention, said micropore titanium-silicon material discloses in application number is 200710064981.6 one Chinese patent application, in the representation of oxide compound; The preferred 0.005-25 of x value, (y+z) are worth preferred 0.01-10, one or more among the preferred Pd of precious metal E, Pt and the Au, 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 with, 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 is all or part of to be hollow 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 low temperature conditioning 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 all or portion be hollow structure, help the diffusion of reactant and product molecule, the synergy of precious metal and HTS is improved, overcome precious metal accumulative drawback.
, application number discloses two kinds of preparing methods of above-mentioned said micropore titanium-silicon material in being 200710064981.6 one Chinese patent application simultaneously.
One of method is HTS, protective material, noble metal source and reductive agent to be joined to change hydrothermal treatment consists in the reaction kettle 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 reaction kettle 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), like 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 Vestolen PP 7052, polyoxyethylene glycol, PS, SE, Vilaterm etc., and tensio-active agent can be AS, 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 80, hydrazine hydrogen chloride, hydrazonium sulfate etc., and hydroborate can be Peng Qinghuana, POTASSIUM BOROHYDRIDE 97MIN 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 salt, 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, Pottasium 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 1-4 carbon atom; Said fat amine compound is ethamine, n-Butyl Amine 99, tetramethylenediamine 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, diethylolamine 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; Do not have 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 filtrating 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 reaction kettle 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, tetramethylenediamine, 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, diethylolamine, trolamine etc.
The said protective material of step (1) is meant polymkeric substance or tensio-active agent; Wherein polymkeric substance can be Vestolen PP 7052, polyoxyethylene glycol, PS, SE, Vilaterm etc., and tensio-active agent can be AS, 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 salt, 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 80, hydrazine hydrogen chloride, hydrazonium sulfate etc., and hydroborate can be Peng Qinghuana, POTASSIUM BOROHYDRIDE 97MIN etc.
The method of catalyzed oxidation hexanaphthene provided by the invention can adopt periodical operation or operate continuously mode.When andnon-continuous operation manner is carried out, behind hexanaphthene, solvent, catalyzer adding reactor drum, add oxygen, hydrogen, diluents continuously; And continuous mode can adopt fixed-bed reactor when carrying out, and behind the catalyzer of packing into solvent, hexanaphthene, oxygen, hydrogen, diluents is added continuously; Also can adopt slurry bed reactor, catalyzer, solvent making beating back are added hexanaphthene, oxygen, hydrogen, diluents 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, hexanaphthene and oxygen, hydrogen, diluents add simultaneously and mix afterreaction in the still.
In the method provided by the invention, the raw material optimum ratio is following: the mol ratio of hexanaphthene and oxygen is preferably 1: (0.2～5.0), the mol ratio of hexanaphthene and hydrogen is preferably 1: (0.2～5.0), the mass ratio of solvent and catalyzer is preferably (0～500): 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 based on actual conditions.
Said diluents 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 compsn that contains micropore titanium-silicon material, and wherein said compsn 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 method of catalyzed oxidation hexanaphthene provided by the invention; In the presence of hydrogen,, need not to add any suppressor factor or initiator in the virgin gas with molecular oxygen as oxidant; Increase the velocity of diffusion of reactant and product, reduced the generation of side reactions such as open loop, over oxidation; The hollow micropore titanium-silicon material that employing contains precious metal, especially contain palladium is as catalytic active component, and cyclohexane conversion is high, selectivity of product is suitable with the steady running time, especially has higher hydrogen effective rate of utilization.
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 done explanation further to 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 on the static n2 absorption apparatus of the ASAP2405 of U.S. Micromeritics company, to measure according to ASTM D4222-98 standard method.
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 the micropore titanium-silicon material A that uses in embodiment 1～8 explanation method provided by the invention, B, 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 80 and cetyl trimethylammonium bromide join TPAOH and mix; HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): Hydrazine Hydrate 80 (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, use water washing, 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).
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 Vestolen PP 7052 join sodium hydroxide and mix; HTS (gram) wherein: Vestolen PP 7052 (mole): sodium hydroxide (mole): hydrazine hydrogen chloride (mole): Palladous chloride (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, use water washing, 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).
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 tetramethylenediamine; Wherein mole is formed the silicon source: titanium source: TPAOH: tetramethylenediamine: palladium source: protective material: water=100: 0.03: 0.5: 0.1: 0.05: 0.02: 550, and 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 filtrating; Added behind an amount of Hydrazine Hydrate 80 under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing; 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 X 2073 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 was 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 filtrating; Added behind the appropriate hydrochloric acid hydrazine under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours; Gains are filtered, use water washing; 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 tetramethylenediamine and mix; HTS (gram) wherein: tween 80 (mole): tetramethylenediamine (mole): Peng Qinghuana (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, use water washing, 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 X 2073 join TPAOH and mix; Add under the high degree of agitation in batches; Continue to stir for some time; HTS (gram) wherein: X 2073 (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, use water washing, 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 acid chloride solution and the cetyl trimethylammonium bromide of 0.01g/ml (in the palladium atom) joins 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 was 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 filtrating; Added behind the appropriate hydrochloric acid hydrazine under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing; 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 80 and cetyl trimethylammonium bromide join TPAOH and mix; HTS (gram) wherein: cetyl trimethylammonium bromide (mole): TPAOH (mole): Hydrazine Hydrate 80 (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, use water washing, after the seasoning; And under 1 80 ℃, 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 explanations utilize dipping method to prepare load type palladium/HTS comparative catalyst's process.
Comparative Examples 1
This Comparative Examples is to utilize the dipping method supported palladium to prepare load type palladium/HTS (0.5%Pd/TS-1) catalyzer.
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, proper seal 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
This Comparative Examples is to utilize the dipping method supported palladium to prepare load type palladium/HTS (2%Pd/TS-1) catalyzer.
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, proper seal 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 process that catalyzer carries out catalyzed oxidation hexanaphthene provided by the invention with the micropore titanium-silicon material A-H of embodiment 1-8 preparation.
Embodiment 9
With hexanaphthene, oxygen (4% volume; All the other are nitrogen), hydrogen, solvent and A be 1: 1: 1 according to the mol ratio of hexanaphthene and oxygen, hydrogen; 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 14%; The hydrogen effective rate of utilization is 36%; Pimelinketone, hexalin selectivity are 95%.
The result who reacts 150 hours is following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 92%.
Embodiment 10
With hexanaphthene, oxygen, hydrogen (10% volume; All the other are argon gas), solvent and B be 1: 2: 1 according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 11%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 93%.
The result who reacts 150 hours is following: cyclohexane conversion is 11%; The hydrogen effective rate of utilization is 33%; Pimelinketone, hexalin selectivity are 93%.
Embodiment 11
With hexanaphthene, oxygen (80% volume; All the other are carbonic acid gas), hydrogen, solvent and C be 1: 5: 2 according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 37%; Pimelinketone, hexalin selectivity are 94%.
The result who reacts 150 hours is following: cyclohexane conversion is 11%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 91%.
Embodiment 12
With hexanaphthene, oxygen, hydrogen (4% volume; All the other are methane), solvent and D be 1: 2: 5 according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 9%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 96%.
The result who reacts 150 hours is following: cyclohexane conversion is 8%; The hydrogen effective rate of utilization is 36%; Pimelinketone, hexalin selectivity are 94%.
Embodiment 13
Is 1: 0.5: 3 with hexanaphthene, oxygen, hydrogen, solvent and E according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 10%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 93%.
The result who reacts 150 hours is following: cyclohexane conversion is 9%; The hydrogen effective rate of utilization is 33%; Pimelinketone, hexalin selectivity are 92%.
Embodiment 14
Is 1: 3: 0.5 with hexanaphthene, oxygen, hydrogen, solvent and F according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 37%; Pimelinketone, hexalin selectivity are 94%.
The result who reacts 150 hours is following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 92%.
Embodiment 15
Present embodiment is to utilize the G of embodiment 7 preparations to do the reaction that catalyzer carries out catalysis cyclohexane oxidation under the hydrogen and oxygen existence; Specific as follows: is 1: 2: 1 with hexanaphthene, oxygen, hydrogen, solvent and G according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 11%; The hydrogen effective rate of utilization is 36%; Pimelinketone, hexalin selectivity are 93%.
The result who reacts 150 hours is following: cyclohexane conversion is 10%; The hydrogen effective rate of utilization is 34%; Pimelinketone, hexalin selectivity are 91%.
Embodiment 16
Is 1: 2: 2 with hexanaphthene, oxygen, hydrogen, solvent and H according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 14%; The hydrogen effective rate of utilization is 37%; Pimelinketone, hexalin selectivity are 94%.
The result who reacts 150 hours is following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 93%.
Embodiment 17
The present embodiment explanation utilizes the A of embodiment 1 preparation to do catalyzer carries out cyclohexane oxidation in the tank reactor of sealing process.
Is 1: 5: 1 with hexanaphthene, oxygen, hydrogen, solvent tertiary butanol and A according to the mol ratio of hexanaphthene and the trimethyl carbinol, oxygen, hydrogen: 1, 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 following: cyclohexane conversion is 15%; The hydrogen effective rate of utilization is 36%; Pimelinketone, hexalin selectivity are 96%.
The result who reacts 150 hours is following: cyclohexane conversion is 27%; The hydrogen effective rate of utilization is 32%; Pimelinketone, hexalin selectivity are 90%.
Embodiment 18
The present embodiment explanation utilizes the B of embodiment 2 preparations to do catalyzer carries out cyclohexane oxidation in the tank reactor of sealing process.
Is 1: 20: 2 with hexanaphthene, oxygen, hydrogen, solvent methanol and B according to the mol ratio of hexanaphthene and methyl alcohol, oxygen, hydrogen: 2, 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 following: cyclohexane conversion is 12%; The hydrogen effective rate of utilization is 35%; Pimelinketone, hexalin selectivity are 96%.
The result who reacts 150 hours is following: cyclohexane conversion is 31%; The hydrogen effective rate of utilization is 32%; Pimelinketone, hexalin selectivity are 91%.
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 hexanaphthene.
Comparative Examples 3
The explanation of this Comparative Examples utilizes the load type palladium/HTS (0.5%Pd/TS-1) of Comparative Examples 1 preparation to make the process that catalyzer carries out the catalyzed oxidation hexanaphthene.
Is 1: 1: 1 with hexanaphthene, oxygen, hydrogen, solvent and catalyzer according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 5%; The hydrogen effective rate of utilization is 16%; Pimelinketone, hexalin selectivity are 95%.
The result who reacts 150 hours is following: cyclohexane conversion is 3%; The hydrogen effective rate of utilization is 15%; Pimelinketone, hexalin selectivity are 91%.
Comparative Examples 4
The explanation of this Comparative Examples utilizes the load type palladium/HTS (2%Pd/TS-1) of Comparative Examples 2 preparations to make the process that catalyzer carries out the catalyzed oxidation hexanaphthene.
Is 1: 1: 1 with hexanaphthene, oxygen, hydrogen, solvent and catalyzer according to the mol ratio of hexanaphthene 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
-1The following reaction.
The result who reacts 2 hours is following: cyclohexane conversion is 6%; The hydrogen effective rate of utilization is 21%; Pimelinketone, hexalin selectivity are 94%.
The result who reacts 150 hours is following: cyclohexane conversion is 3%; The hydrogen effective rate of utilization is 18%; Pimelinketone, hexalin selectivity are 91%.
Can find out from the reaction result of embodiment 9-18 and Comparative Examples 3,4: method cyclohexane conversion of the present invention is high, selectivity of product is suitable with the steady running time, especially has higher hydrogen effective rate of utilization.
Claims (11)
1. the method for a catalyzed oxidation hexanaphthene; It is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure; With hexanaphthene, oxygen, hydrogen, diluents, solvent and catalyst mix contact reacts; The mol ratio of hexanaphthene and oxygen, hydrogen, diluents is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of hexanaphthene and catalyzer are (0.5-50): 1, and the mass ratio of solvent and catalyzer is (0～1000): 1; Said catalyzer is a kind of micropore titanium-silicon material or the compsn 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, and E representes to be selected from the precious metal of Pt and/or Pd, and m and n satisfy the required number of E oxidation state, and this material grains partly or entirely is a hollow structure.
2. 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.
3. according to the method for claim 1, it is characterized in that the said compsn 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.
4. according to the method for claim 1, it is characterized in that said diluents is selected from nitrogen, argon gas, helium, neon, perhaps is selected from carbonic acid gas, methane, ethane, propane.
5. according to the method for claim 1, the mol ratio that it is characterized in that said hexanaphthene and oxygen is 1: (0.2～5.0), the mol ratio of hexanaphthene and hydrogen are 1: (0.2～5.0), the mass ratio of solvent and catalyzer are (0～500): 1.
6. 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.
7. 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.
8. according to the method for claim 7, it is characterized in that said alcohol is methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol or isopropylcarbinol, said ketone is acetone, butanone, and said nitrile is an acetonitrile.
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
11. according to the method for claim 10, the total gas space velocity of said reaction is 100～5000h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710175280XA CN101397235B (en) | 2007-09-28 | 2007-09-28 | Method for catalytic oxidation of cyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710175280XA CN101397235B (en) | 2007-09-28 | 2007-09-28 | Method for catalytic oxidation of cyclohexane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101397235A CN101397235A (en) | 2009-04-01 |
| CN101397235B true CN101397235B (en) | 2012-02-15 |
Family
ID=40516103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710175280XA Active CN101397235B (en) | 2007-09-28 | 2007-09-28 | Method for catalytic oxidation of cyclohexane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101397235B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382025B (en) * | 2010-08-31 | 2014-10-29 | 中国石油化工股份有限公司 | Method for oxidizing naphthenic hydrocarbon |
| CN102452895B (en) * | 2010-10-29 | 2015-03-18 | 中国石油化工股份有限公司 | Method for catalyzing cycloalkane by utilizing Sn-containing Ti-Si molecular sieve |
| CN109701549B (en) * | 2017-10-26 | 2022-03-29 | 中国石油化工股份有限公司 | Catalyst for preparing methyl isobutyl ketone by acetone one-step method and preparation method and application thereof |
| CN113877607A (en) * | 2021-09-13 | 2022-01-04 | 浙江师范大学 | Platinum-supported solid acid low-carbon alkane oxidation catalyst, and preparation method and application thereof |
| CN114247441B (en) * | 2021-11-23 | 2024-02-13 | 中海油天津化工研究设计院有限公司 | Catalyst for preparing 1,2,4, 5-cyclohexane tetracarboxylic dianhydride by hydrogenation of pyromellitic anhydride and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772723A (en) * | 2004-11-12 | 2006-05-17 | 中国科学院兰州化学物理研究所 | Selective oxidation process of cyclohexane to prepare cyclohexanone |
| CN1781889A (en) * | 2004-11-30 | 2006-06-07 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanol and cyclohexanone by oxidizing cyclohexane |
-
2007
- 2007-09-28 CN CN200710175280XA patent/CN101397235B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772723A (en) * | 2004-11-12 | 2006-05-17 | 中国科学院兰州化学物理研究所 | Selective oxidation process of cyclohexane to prepare cyclohexanone |
| CN1781889A (en) * | 2004-11-30 | 2006-06-07 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanol and cyclohexanone by oxidizing cyclohexane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101397235A (en) | 2009-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2459661C2 (en) | Noble metal-bearing titanium-silicate material and method of its production | |
| CN101314577B (en) | Method for catalysis of pimelinketone oxamidine | |
| CN101434587B (en) | Method for synthesizing epoxy styrene by catalytic oxidation of phenylethylene | |
| CN101397235B (en) | Method for catalytic oxidation of cyclohexane | |
| CN101314583B (en) | Method for catalytic oxidation of tert-butanol | |
| CN101654256B (en) | Method for in situ synthesis of titanium-silicon molecular sieve material containing noble metal | |
| CN101434586B (en) | Propylene chloride epoxidation process in the presence of hydrogen and oxygen | |
| CN101397240B (en) | Method for preparing p-dihydroxy benzene and pyrocatechol by phenol hydroxylation | |
| CN101665256B (en) | Method for treating titanium silicate molecular sieve by using noble metal source | |
| CN101683984B (en) | Method for synthesizing titanium silicon materials containing noble metal | |
| CN101570523B (en) | Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol | |
| CN101397283B (en) | Method for producing epoxypropane by catalytic epoxidation of propone | |
| CN101643459B (en) | Method for preparing 1,2-butylene oxide | |
| CN101570509B (en) | Method for preparing pyridine N-oxide | |
| CN101544582B (en) | Synthetic method of diacetylmonoxime | |
| CN103183357B (en) | The modified with noble metals method of HTS | |
| CN103183356B (en) | Method for modifying titanium silicalite molecular sieve by precious metal source | |
| CN101434515B (en) | Method for preparing phenol | |
| CN101683986B (en) | Preparation method of titanium-silicon material | |
| CN101481119B (en) | Micropore titanium silicon molecular sieve material and preparation thereof | |
| CN101544620B (en) | Preparation method of epoxy cyclohexane | |
| CN105293517A (en) | Titanium-silicon molecular sieve and preparation method and application thereof, and method for direct oxidation of olefin | |
| CN101683985B (en) | Method for in situ synthesizing titanium silicon materials containing noble metal |
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 |