CN102766037B - Method for preparing adipic acid from cyclohexene - Google Patents
Method for preparing adipic acid from cyclohexene Download PDFInfo
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- CN102766037B CN102766037B CN201110117266.0A CN201110117266A CN102766037B CN 102766037 B CN102766037 B CN 102766037B CN 201110117266 A CN201110117266 A CN 201110117266A CN 102766037 B CN102766037 B CN 102766037B
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Abstract
The invention provides a method for preparing adipic acid from cyclohexene. According to the method, cyclohexene and hydrogen peroxide contact with a catalyst under the condition of oxidation reaction. The catalyst contains an ingredient A and an ingredient B, wherein the ingredient A is a titanium silicalite molecular sieve; and the ingredient B contains one or more selected from polymetallic oxyacid and polyoxometalates. The method for preparing adipic acid from cyclohexene has advantages of mild operation condition, little equipment corrosion and environmental protection, and has high selectivity of adipic acid. In addition, the catalyst used in the method has high active stability, and can still maintain a high catalytic activity even used for a long time.
Description
Technical field
The present invention relates to a kind of method of being prepared hexanodioic acid by tetrahydrobenzene.
Background technology
Hexanodioic acid is a kind of important Chemicals, and tool has been widely used.For example: hexanodioic acid is synthon---the main raw material of nylon 66 and nylon series engineering plastics is also the raw material of synthesis of polyurethane foam, Synthetic Leather, synthetic rubber and film simultaneously; Hexanodioic acid can be used as food acidulant, ester plasticizer and textile treating agent, also can be used for the production of medicine, agricultural chemicals, spices, tackiness agent and soldering flux etc.
In traditional Production Processes of Adipic Acid, be mainly taking benzene as starting raw material, first hydrogenation is to prepare hexanaphthene; Then carry out atmospheric oxidation, cyclohexane oxidation is become to hexalin and pimelinketone (being commonly called as K-A oil); Then with nitric acid, K-A oil is oxidized to hexanodioic acid.This route accounts for the more than 90% of global hexanodioic acid aggregated capacity.The at present industrialized method by oxidation hexalin and Cyclohexanone Production hexanodioic acid is derived from the technique of E.I.Du Pont Company in the exploitation forties in 20th century, at 70-90 DEG C, use concentrated nitric acid and copper catalyst or vanadium catalyst catalyzed oxidation hexalin and the pimelinketone of 40-60%, thereby produce hexanodioic acid.The deficiency of this technique is: need to use concentrated nitric acid, operational condition harshness, seriously polluted to equipment corrosion on the other hand on the one hand, also can produce in addition the nitrogenous compound that environment is had to severe contamination.
Therefore, develop a kind of operational condition gentleness, to the corrosion of equipment, the little and eco-friendly novel process of preparing hexanodioic acid is of great practical significance.
Summary of the invention
The object of the present invention is to provide a kind of operational condition gentleness, to the corrosion of equipment little and environmental friendliness, also hexanodioic acid is there is the preparation method of higher optionally hexanodioic acid simultaneously.
HTS is a kind of novel catalyzed oxidation material of developing last century 80, adopts HTS to have following remarkable advantage as catalyzer: (1) reaction conditions gentleness, can under normal pressure, low temperature (20-100 DEG C), carry out; (2) target product selectivity is good; (3) technological process is simple, environmental friendliness.But, the present inventor is studying using tetrahydrobenzene as raw material, prepare taking HTS as catalyzer in the process of hexanodioic acid and find, in any case optimize various processing parameters in this process (as selected suitable solvent, optimize the condition of oxidizing reaction etc.), all cannot obtain gratifying cyclohexene conversion rate and hexanodioic acid selectivity.Through further investigation, the present inventor surprisingly finds: the salt of introducing multiple-metal oxygen-containing acid and/or multiple-metal oxygen-containing acid in this process can improve the selectivity of transformation efficiency and the hexanodioic acid of tetrahydrobenzene greatly.Complete thus the present invention.
The invention provides a kind of method of being prepared hexanodioic acid by tetrahydrobenzene, the method comprises: under oxidation reaction condition, tetrahydrobenzene is contacted with catalyzer with hydrogen peroxide, wherein, described catalyzer contains component A and B component, described component A is HTS, and described B component is one or more in the salt of multiple-metal oxygen-containing acid and multiple-metal oxygen-containing acid.
The method of being prepared hexanodioic acid by tetrahydrobenzene provided by the invention, operational condition gentleness, the little and environmental friendliness to equipment corrosion.And the method according to this invention has higher selectivity for hexanodioic acid.In addition, the activity stability of the catalyzer using in the method according to this invention is high, even if long-time use also can keep higher catalytic activity.
Embodiment
The invention provides a kind of method of being prepared hexanodioic acid by tetrahydrobenzene, the method comprises: under oxidation reaction condition, tetrahydrobenzene is contacted with catalyzer with hydrogen peroxide, wherein, described catalyzer contains component A and B component, described component A is HTS, and described B component is one or more in the salt of multiple-metal oxygen-containing acid and multiple-metal oxygen-containing acid.
According to the inventive method, by by tetrahydrobenzene and hydrogen peroxide contain HTS and be selected from multiple-metal oxygen-containing acid and the salt of multiple-metal oxygen-containing acid at least one the existence of catalyzer under, under oxidation reaction condition, contact, can obtain high cyclohexene conversion rate and hexanodioic acid selectivity on the one hand; On the other hand the operational condition gentleness of the method, to equipment corrosion little and environmental friendliness; In addition, described catalyzer has higher activity stability, even if use for a long time, still can keep higher catalytic activity.
The method according to this invention, described catalyzer contains component A and B component, and wherein, component A is HTS, and B component is one or more in the salt of multiple-metal oxygen-containing acid and multiple-metal oxygen-containing acid.In the present invention, described B component can be one or more in multiple-metal oxygen-containing acid; Also can be one or more in the salt of multiple-metal oxygen-containing acid; It can also be the combination of the salt of one or more multiple-metal oxygen-containing acid and one or more multiple-metal oxygen-containing acid.In the time that described B component is the combination of salt of one or more multiple-metal oxygen-containing acid and one or more multiple-metal oxygen-containing acid, the anionicsite of described multiple-metal oxygen-containing acid can be identical with the anionicsite of the salt of described multiple-metal oxygen-containing acid, also can be different.
In the present invention, described HTS can be the HTS of various routines, for example: described HTS can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.Preferably, described HTS is the HTS (as TS-1) of MFI structure and/or the HTS (as Ti-Beta) of BEA structure.Further preferably, the HTS (as TS-1) that described HTS is MFI structure.Above-mentioned molecular sieve can be commercially available, or adopts method well known in the art synthetic, repeats no more herein.
The method according to this invention, described HTS most preferably is the HTS of MFI structure, and the crystal grain of described HTS is hollow structure, the radical length of the cavity part of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recording under the condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, has hysteresis loop.Hereinafter, the HTS of the type is called to hollow HTS.In the time that described HTS is above-mentioned hollow HTS, the method according to this invention, not only can obtain higher cyclohexene conversion rate and hexanodioic acid selectivity, and the catalyzer that contains described hollow HTS has more excellent activity stability.
In the present invention, described multiple-metal oxygen-containing acid refers to the oxygen acid cluster compound that multiple metal oxygen-containing acid molecules form by dehydrating condensation, for example: polyacid.The method according to this invention, described multiple-metal oxygen-containing acid can be conventional various multiple-metal oxygen-containing acid, for example: described multiple-metal oxygen-containing acid can be heteropolyacid and/or isopoly-acid.Described heteropolyacid is well known to those skilled in the art, and the class generally consisting of oxygen atom ligand bridging by certain structure heteroatoms (as P, Si, Fe, Co etc.) and many atoms metals (as Mo, W, V, Nb, Ta etc.) is containing oxygen polyacid.In the present invention, described isopoly-acid refers to the acid that two or more simple oxygen acid molecule of the same race condensations form, and the specific examples of described isopoly-acid can be but be not limited to: H
4v
2o
7, H
6v
4o
13, H
7v
5o
16, H
6v
10o
2, H
6mo
7o
24, H
4mo
8o
26and H
10mo
12o
41in one or more.
In the present invention, the salt of described multiple-metal oxygen-containing acid can be the salt of common various multiple-metal oxygen-containing acid, for example: by the one or more hydrogen ions in described multiple-metal oxygen-containing acid are replaced to the salt of the multiple-metal oxygen-containing acid forming with ammonium radical ions or metal ion.In the present invention, the salt of described multiple-metal oxygen-containing acid can be the salt of heteropolyacid and/or the salt of isopoly-acid; Described metal ion can be one or more in ammonium radical ion, alkalimetal ion and alkaline-earth metal ions.
In the present invention, the salt of described heteropolyacid and heteropolyacid comprises the heteropoly blue salt of heteropolyacid or heteropolyacid being reduced and obtain separately.Described heteropoly blue can be obtained by the salt reduction of heteropolyacid or heteropolyacid conventionally, for example: phospho-molybdic acid can obtain blue phosphorus molybdenum blue with Reduction with Stannous Chloride, other heteropoly blue also can obtain by reducing the salt of its corresponding heteropolyacid or heteropolyacid, and this is no longer going to repeat them.
The structure of the salt of the present invention to described heteropolyacid and heteropolyacid is without particular requirement, can be the heteropolyacid of various structures or the salt of heteropolyacid, for example: the salt of described heteropolyacid and heteropolyacid can be Keggin structure, Dawson structure, Silverton structure, Waugh structure or Anderson structure separately.
The method according to this invention, described B component can be one or more in the salt of heteropolyacid, isopoly-acid, heteropolyacid and the salt of isopoly-acid.From the angle of being easy to get property of raw material, described B component is preferably one or more in ammonium salt, an alkali metal salt of isopoly-acid and the alkaline earth salt of isopoly-acid of alkaline earth salt, isopoly-acid of an alkali metal salt, the heteropolyacid of ammonium salt, the heteropolyacid of heteropolyacid, isopoly-acid, heteropolyacid.
The present inventor finds in research process, when the IVB family metallic element of respectively doing for oneself of the metallic element in the salt of the metallic element in described heteropolyacid and described heteropolyacid, VB family metallic element, one or more in group vib metallic element and VIIB family metallic element, metallic element in metallic element in described isopoly-acid and the salt of the described isopoly-acid IVB family metallic element of respectively doing for oneself, VB family metallic element, when a kind of in group vib metallic element and VIIB family metallic element, can further improve the activity of the catalyzer using in the method according to this invention, thereby further improve the selectivity of transformation efficiency and the hexanodioic acid of tetrahydrobenzene.Metallic element in metallic element in described heteropolyacid and the salt of described heteropolyacid can be for example one or more in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium and rhenium separately, and the metallic element in the metallic element in described isopoly-acid and the salt of described isopoly-acid can be for example the one in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium and rhenium separately.
Preferably, respectively do for oneself one or more in VB family metallic element and group vib metallic element of metallic element in metallic element in described heteropolyacid and the salt of described heteropolyacid, the one that the metallic element in the metallic element in described isopoly-acid and the salt of described isopoly-acid is respectively done for oneself in VB family metallic element and group vib metallic element.
More preferably, respectively do for oneself one or more in molybdenum, tungsten, vanadium, chromium, tantalum and niobium of metallic element in metallic element in described heteropolyacid and the salt of described heteropolyacid, the one that the metallic element in the metallic element in described isopoly-acid and the salt of described isopoly-acid is respectively done for oneself in molybdenum, tungsten, vanadium, chromium, tantalum and niobium.
One of the present invention preferred embodiment in, described B component is one or more in the salt of the salt of the salt of the salt of salt, the molybdenum vanadium heteropolyacid of salt, the phosphorus vanadium heteropolyacid of salt, the phosphato-molybdic heteropolyacid of phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, the isopoly-acid being formed by molybdenum, the isopoly-acid being formed by tungsten, the isopoly-acid being formed by vanadium, phosphorus heteropoly tungstic acid, the isopoly-acid that formed by molybdenum, the isopoly-acid that formed by tungsten and the isopoly-acid that formed by vanadium.
One of the present invention more preferred embodiment in, described B component is phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, the isopoly-acid being formed by molybdenum, the isopoly-acid being formed by tungsten, the isopoly-acid being formed by vanadium, the ammonium salt of phosphorus heteropoly tungstic acid, the an alkali metal salt of phosphorus heteropoly tungstic acid, the alkaline earth salt of phosphorus heteropoly tungstic acid, the ammonium salt of phosphato-molybdic heteropolyacid, the an alkali metal salt of phosphato-molybdic heteropolyacid, the alkaline earth salt of phosphato-molybdic heteropolyacid, the ammonium salt of phosphorus vanadium heteropolyacid, the an alkali metal salt of phosphorus vanadium heteropolyacid, the alkaline earth salt of phosphorus vanadium heteropolyacid, the ammonium salt of molybdenum vanadium heteropolyacid, the an alkali metal salt of molybdenum vanadium heteropolyacid, the alkaline earth salt of molybdenum vanadium heteropolyacid, the ammonium salt of the isopoly-acid being formed by molybdenum, the an alkali metal salt of the isopoly-acid being formed by molybdenum, the alkaline earth salt of the isopoly-acid being formed by molybdenum, the ammonium salt of the isopoly-acid being formed by tungsten, the an alkali metal salt of the isopoly-acid being formed by tungsten, the alkaline earth salt of the isopoly-acid being formed by tungsten, the ammonium salt of the isopoly-acid being formed by vanadium, one or more in the alkaline earth salt of an alkali metal salt of the isopoly-acid being formed by vanadium and the isopoly-acid that formed by vanadium.
The method according to this invention, the component A in described catalyzer and the ratio of B component can change in wide in range scope.Preferably, by weight, the ratio of the amount of described component A and the amount of described B component is 0.05-200: 1.From further raising cyclohexene conversion rate and optionally angle of oxalic acid, by weight, the more preferably 0.1-100 of ratio of the amount of described component A and the amount of described B component: 1.
The method according to this invention is used hydrogen peroxide as oxygenant.In the present invention, described hydrogen peroxide can be the hydrogen peroxide existing with the various forms of this area routine.From the angle of the security of further raising the method according to this invention, the method according to this invention is preferably used the hydrogen peroxide existing with aqueous solution form.The method according to this invention, in the time that described hydrogen peroxide provides with aqueous solution form, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, for example: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method preparation, also can be commercially available, for example: can be hydrogen peroxide, the hydrogen peroxide of 50 % by weight or the hydrogen peroxide of 70 % by weight of 30 % by weight that can be commercially available.The hydrogen peroxide using in the embodiment of the present invention and comparative example for concentration be the hydrogen peroxide of 30 % by weight.
The method according to this invention, tetrahydrobenzene can carry out with contacting of hydrogen peroxide under solvent exists, and can make the method according to this invention have higher security so on the one hand, can also make on the other hand the contact of each reactant more abundant.The present invention is not particularly limited for the kind of described solvent, can be the conventional all kinds of SOLVENTS in this area.Preferably, described solvent is water, C
1-C
10alcohol, C
3-C
10ketone and C
2-C
10nitrile in one or more, for example: one or more in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.More preferably, described solvent is water, C
1-C
5alcohol, C
3-C
5ketone and C
2-C
5nitrile in one or more, for example: one or more in acetonitrile, acetone, first alcohol and water.
The method according to this invention, tetrahydrobenzene can carry out with contacting of hydrogen peroxide under oxygen-containing atmosphere, also can under anoxic condition, carry out.In embodiments of the invention and comparative example, tetrahydrobenzene carries out under air atmosphere with contacting all of hydrogen peroxide.
The method according to this invention is not particularly limited for the consumption of solvent, can be the conventional amount used of this area.Preferably, the weight ratio of described solvent and catalyzer is 1-200: 1.More preferably, the weight ratio of described solvent and catalyzer is 10-200: 1.
The method according to this invention is not particularly limited for described oxidation reaction condition.Usually, described oxidation reaction condition comprises: the mol ratio of tetrahydrobenzene and hydrogen peroxide can be 1: 0.1-10, is preferably 1: 0.2-5; The weight ratio of tetrahydrobenzene and described catalyzer can be 1-200: 1, be preferably 1-100: 1; Temperature can be 20-160 DEG C, is preferably 20-120 DEG C, more preferably 30-90 DEG C; Pressure can be 0.1-2.5MPa, is preferably 0.1-1.5MPa.
The method according to this invention, can adopt periodical operation, also can adopt operate continuously etc., the present invention to this without particular requirement.Feed way can be also any suitable way well known by persons skilled in the art, as in the time that andnon-continuous operation manner is carried out, solvent and catalyzer can be added after reactor, adds continuously tetrahydrobenzene and hydrogen peroxide to react; Carry out rhythmic reaction in closed tank reactor time, catalyzer, solvent, tetrahydrobenzene and hydrogen peroxide can be added to hybrid reaction in still simultaneously.When continuous mode carries out, can adopt the reactor that fixed-bed reactor or slurry bed reactor etc. are conventional, while carrying out in fixed-bed reactor, feed way can add solvent, tetrahydrobenzene and hydrogen peroxide continuously packing into after catalyzer; While carrying out in slurry bed reactor, can will after catalysts and solvents making beating, add continuously tetrahydrobenzene, hydrogen peroxide to react; The present invention, does not repeat at this all without particular requirement one by one to this.
The method according to this invention can adopt the ordinary method of this area that hexanodioic acid is separated from the product of contact of tetrahydrobenzene and hydrogen peroxide, for example: can be by product of contact is carried out to fractionation, thus hexanodioic acid is separated from reaction product.The method of described fractionation and condition are known in the field, repeat no more herein.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.
In following examples and comparative example, if not otherwise specified, reagent used is commercially available analytical reagent.
In following examples, titanium-silicon molecular sieve TS-1 used is according to Zeolites, 1992, the 12 volumes, and prepared by the method described in 943-950 page, and in oxide compound, the titanium content in this HTS is 2.4 % by weight.
In following examples, hollow HTS HTS used is that the Industrial products of HTS (are purchased and build feldspathization stock company from Hunan, through X-ray diffraction analysis, be defined as the HTS of MFI structure described in Chinese patent CN1301599A; Between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, have hysteresis loop, crystal grain is that the radical length of hollow crystal grain and cavity part is 15-180 nanometer; This HTS sample is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 78 milligrams/gram), in oxide compound, the titanium content in this HTS is 2.5 % by weight.
In following examples, HTS Ti-MCM-41 used be according to Corma etc. at Chem.Commun., prepared by the method described in 1994,147-148, in oxide compound, the titanium content in this HTS is 3 % by weight.
In following examples, HTS Ti-Beta used be according to Takashi Tatsumi etc. at J.Chem.Soc.Chem.Commun., prepared by the method described in 1997,677-678, in oxide compound, the titanium content in this HTS is 2.6 % by weight.
In the present invention, adopt vapor-phase chromatography to carry out the content of each composition in analysis system, adopt respectively on this basis following formula to carry out the selectivity of transformation efficiency and the hexanodioic acid of ring hexene:
Embodiment 1
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 30 DEG C and pressure are under 1.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and methyl alcohol reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and phospho-wolframic acid
3pW
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and phospho-wolframic acid is 100: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 2; Methyl alcohol is 20: 1 with catalyst quality ratio; The mass ratio of tetrahydrobenzene and catalyzer is 20: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 36%, and hexanodioic acid selectivity is 87%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 29%, and hexanodioic acid selectivity is 82%.
Embodiment 2
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 30 DEG C and pressure are under 1.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and methyl alcohol reacted in autoclave, wherein, described catalyzer is that (molecular formula is H for TS-1 and phospho-wolframic acid
3pW
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and phospho-wolframic acid is 0.1: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 3; The mass ratio of methyl alcohol and catalyzer is 120: 1; The mass ratio of tetrahydrobenzene and catalyzer is 40: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 47%, and hexanodioic acid selectivity is 84%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 44%, and hexanodioic acid selectivity is 81%.
Embodiment 3
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 60 DEG C and pressure are under 1.0MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and acetone reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and phospho-wolframic acid
3pW
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and phospho-wolframic acid is 50: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 5; The mass ratio of acetone and catalyzer is 200: 1; The mass ratio of tetrahydrobenzene and catalyzer is 80: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 43%, and hexanodioic acid selectivity is 82%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 40%, and hexanodioic acid selectivity is 78%.
Embodiment 4
The present embodiment be used for explanation according to of the present invention prepare hexanodioic acid by tetrahydrobenzene and method.
Be that 40 DEG C and pressure are under 0.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and the trimethyl carbinol reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and phospho-molybdic acid
3pMo
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and phospho-molybdic acid is 10: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 4; The mass ratio of the trimethyl carbinol and catalyzer is 80: 1; The mass ratio of tetrahydrobenzene and catalyzer is 2: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 28%, and hexanodioic acid selectivity is 90%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 25%, and hexanodioic acid selectivity is 86%.
Embodiment 5
The present embodiment be used for explanation according to of the present invention prepare hexanodioic acid by tetrahydrobenzene and method.
Be that 90 DEG C and pressure are under 1.0MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and water reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and phosphorus tungsten heteropoly blue
5pW
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and phosphorus tungsten heteropoly blue is 20: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 3; The mass ratio of water and catalyzer is 180: 1; The mass ratio of tetrahydrobenzene and catalyzer is 5: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 37%, and hexanodioic acid selectivity is 88%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 32%, and hexanodioic acid selectivity is 85%.
Embodiment 6
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 40 DEG C and pressure are under 0.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and methyl alcohol reacted in autoclave.Wherein, described catalyzer is that (molecular formula is (NH for TS-1 and ammonium phosphomolybdate
3)
3pMo
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and ammonium phosphomolybdate is 20: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 0.6; The mass ratio of methyl alcohol and catalyzer is 10: 1; The mass ratio of tetrahydrobenzene and catalyzer is 10: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 51%, and hexanodioic acid selectivity is 86%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 46%, and hexanodioic acid selectivity is 84%.
Embodiment 7
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 40 DEG C and pressure are under 0.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and acetone reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and silicotungstic acid
3siW
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and silicotungstic acid is 15: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 3: 1; The mass ratio of acetone and catalyzer is 80: 1; The mass ratio of tetrahydrobenzene and catalyzer is 100: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 31%, and hexanodioic acid selectivity is 90%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 30%, and hexanodioic acid selectivity is 84%.
Embodiment 8
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 60 DEG C and pressure are under 0.6MPa in temperature, under catalyzer exists, tetrahydrobenzene, acetone and hydrogen peroxide reacted in autoclave.Wherein, described catalyzer is that (molecular formula is H for TS-1 and ten vanadic acid
6v
10o
28, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and ten vanadic acid is 10: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 4; The mass ratio of acetone and catalyzer is 50: 1; The mass ratio of tetrahydrobenzene and catalyzer is 20: 1.Respectively the reaction solution and the reaction reaction solution of 12 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 46%, and hexanodioic acid selectivity is 85%.The result of reacting 12 hours is as follows: cyclohexene conversion rate is 41%, and hexanodioic acid selectivity is 82%.
Embodiment 9
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 6 to prepare hexanodioic acid, different, TS-1 is replaced by HTS.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 55%, and hexanodioic acid selectivity is 87%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 54%, and hexanodioic acid selectivity is 87%.
Embodiment 10
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 6 to prepare hexanodioic acid, different, TS-1 is replaced by Ti-MCM-41.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 43%, and hexanodioic acid selectivity is 82%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 36%, and hexanodioic acid selectivity is 80%.
Embodiment 11
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 6 to prepare hexanodioic acid, different, TS-1 is replaced by Ti-Beta.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 48%, and hexanodioic acid selectivity is 86%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 45%, and hexanodioic acid selectivity is 83%.
Embodiment 12
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 1 to prepare hexanodioic acid, different, the mass ratio of TS-1 and phospho-wolframic acid is 200: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 34%, and hexanodioic acid selectivity is 85%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 26%, and hexanodioic acid selectivity is 81%.
Embodiment 13
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 2 to prepare hexanodioic acid, different, the mass ratio of TS-1 and phospho-wolframic acid is 0.05: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 31%, and hexanodioic acid selectivity is 81%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 24%, and hexanodioic acid selectivity is 76%.
Embodiment 14
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Adopt the method identical with embodiment 2 to prepare hexanodioic acid, different, replace methyl alcohol with acetic acid.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 42%, and hexanodioic acid selectivity is 83%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 35%, and hexanodioic acid selectivity is 79%.
Embodiment 15
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 80 DEG C and pressure are under 0.1MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and acetone reacted in autoclave.Wherein, described catalyzer is that TS-1 and sodium phosphomolybdate are that (molecular formula is Na
3pMo
12o
40, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and sodium phosphomolybdate is 20: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 2: 1; The mass ratio of acetone and catalyzer is 40: 1; The mass ratio of tetrahydrobenzene and catalyzer is 10: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 36%, and hexanodioic acid selectivity is 79%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 34%, and hexanodioic acid selectivity is 77%.
Embodiment 16
The present embodiment is used for explanation according to the method for being prepared hexanodioic acid by tetrahydrobenzene of the present invention.
Be that 60 DEG C and pressure are under 0.5MPa in temperature, under catalyzer exists, tetrahydrobenzene, hydrogen peroxide and acetonitrile reacted in autoclave.Wherein, described catalyzer is that (molecular formula is K for TS-1 and many potassium wolframates
2w
6o
19, be purchased from chemical reagents corporation of traditional Chinese medicines group), and the mass ratio of TS-1 and many potassium wolframates is 10: 1; The mol ratio of tetrahydrobenzene and hydrogen peroxide is 1: 1; The mass ratio of acetonitrile and catalyzer is 20: 1; The mass ratio of tetrahydrobenzene and catalyzer is 20: 1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows: cyclohexene conversion rate is 41%, and hexanodioic acid selectivity is 81%.The result of reacting 15 hours is as follows: cyclohexene conversion rate is 38%, and hexanodioic acid selectivity is 80%.
Comparative example 1
Be that 30 DEG C of pressure are under 1.5MPa in temperature, tetrahydrobenzene, hydrogen peroxide and acetone are reacted in autoclave.Wherein, the mol ratio of tetrahydrobenzene, hydrogen peroxide and acetone is 1: 2: 5.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows, and the transformation efficiency of tetrahydrobenzene is 0.6%, and hexanodioic acid selectivity is 0%.The result of reacting 15 hours is as follows: the transformation efficiency of tetrahydrobenzene is 0.9%, and hexanodioic acid selectivity is 0%.
Comparative example 2
Adopt the method identical with embodiment 1 to prepare hexanodioic acid, different, catalyzer is TS-1.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows, and the transformation efficiency of tetrahydrobenzene is 13%, and hexanodioic acid selectivity is 3%.The result of reacting 15 hours is as follows: the transformation efficiency of tetrahydrobenzene is 11%, and hexanodioic acid selectivity is 1%.
Comparative example 3
Adopt the method identical with embodiment 1 to prepare hexanodioic acid, different, catalyzer is phospho-wolframic acid.Respectively the reaction solution and the reaction reaction solution of 15 hours that react 2 hours are analyzed.The result of reacting 2 hours is as follows, and the transformation efficiency of tetrahydrobenzene is 8%, and hexanodioic acid selectivity is 26%.The result of reacting 15 hours is as follows: the transformation efficiency of tetrahydrobenzene is 6%, and hexanodioic acid selectivity is 15%.
Embodiment 1-16 is compared and can be found out with comparative example 1-3 respectively, adopt method of the present invention to prepare hexanodioic acid by tetrahydrobenzene, can obtain high hexanodioic acid selectivity and higher cyclohexene conversion rate.
Claims (9)
1. prepared the method for hexanodioic acid by tetrahydrobenzene for one kind, the method comprises: under oxidation reaction condition, tetrahydrobenzene is contacted with catalyzer with hydrogen peroxide, it is characterized in that, described catalyzer contains component A and B component, described component A is HTS, and described B component is one or more in the salt of multiple-metal oxygen-containing acid and multiple-metal oxygen-containing acid, and the salt of described multiple-metal oxygen-containing acid is that one or more hydrogen ions ammonium radical ions or the metal ion replacement in multiple-metal oxygen-containing acid forms; By weight, the ratio of the amount of described component A and the amount of described B component is 0.05-200:1; Described B component is one or more in the salt of the salt of the salt of the salt of salt, the molybdenum vanadium heteropolyacid of salt, the phosphorus vanadium heteropolyacid of salt, the phosphato-molybdic heteropolyacid of phosphorus heteropoly tungstic acid, phosphato-molybdic heteropolyacid, phosphorus vanadium heteropolyacid, molybdenum vanadium heteropolyacid, the isopoly-acid being formed by molybdenum, the isopoly-acid being formed by tungsten, the isopoly-acid being formed by vanadium, phosphorus heteropoly tungstic acid, the isopoly-acid that formed by molybdenum, the isopoly-acid that formed by tungsten and the isopoly-acid that formed by vanadium.
2. method according to claim 1, wherein, by weight, the ratio of the amount of described component A and the amount of described B component is 0.1-100:1.
3. method according to claim 1 and 2, wherein, described metal ion is alkalimetal ion and/or alkaline-earth metal ions.
4. method according to claim 1 and 2, wherein, described HTS is at least one in HTS, the HTS of TUN structure and the HTS of two-dimentional hexagonal structure of HTS, MOR structure of HTS, the MWW structure of HTS, the BEA structure of HTS, the MEL structure of MFI structure.
5. method according to claim 4, wherein, described HTS is the HTS of MFI structure, the crystal grain of described HTS is hollow structure, the radical length of the cavity part of this hollow structure is 5-300 nanometer, and described HTS is that the benzene adsorptive capacity recording under the condition of 1 hour is at least 70 milligrams/grams at 25 DEG C, P/P0=0.10, adsorption time, between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, has hysteresis loop.
6. method according to claim 1, wherein, described contact is carried out in solvent, and the weight ratio of described solvent and catalyzer is 1-200:1.
7. method according to claim 6, wherein, described solvent is one or more in alcohol, the ketone of C3-C10 and the nitrile of C2-C10 of water, C1-C10.
8. method according to claim 7, wherein, described solvent is one or more in water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.
9. according to the method described in claim 1 or 6, wherein, described hydrogen peroxide provides with aqueous hydrogen peroxide solution, described oxidation reaction condition comprises: the mol ratio of tetrahydrobenzene and hydrogen peroxide is 1:0.1-10, the weight ratio of tetrahydrobenzene and described catalyzer is 1-200:1, temperature is 20-160 DEG C, and pressure is 0.1-2.5MPa.
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