CN101239899A - Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method - Google Patents
Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method Download PDFInfo
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Abstract
The invention discloses a method for preparing adipic acid by one step of catalysis and oxidation of cyclohexane. The method comprises: firstly adding cyclohexane, a solvent, an initiator and a solid catalyst into a reactor to mix, forming a mixing suspension; rising the temperature of the formed mixing suspension to 50-250 DEG C, insufflating abundant oxygen or air as the oxidant, setting the pressure of the reactor is 0.1-5 MPa, the reaction time is 0.1-20h; separating the reaction mixture to obtain the solid catalyst, and a liquid mixture contained reacted products, un-reacted products and the solvent; and finally separating adipic acid from the separated liquid phase mixture. The invention avoids environmental pollution due to use of nitric acid, and device corrosion; solves the problem that the homogeneous catalyst is difficult to recovery during cyclohexane oxidation; has high reaction selectivity and good activity. The catalyst used in the invention can be recoveried and recycled.
Description
Technical field
The present invention relates to the preparation method of hexanodioic acid, particularly relate to the method that a kind of one step of catalyzed oxidation by hexanaphthene prepares hexanodioic acid.
Background technology
Hexanodioic acid is the important source material of preparation urethane and nylon 66, also is the intermediate of many lubricating oil additives simultaneously.In traditional Production Processes of Adipic Acid, mainly be with benzene as starting raw material, at first through producing cyclohexane by adding hydrogen, reoxidize hexanaphthene and become hexalin and pimelinketone (KA oil), with nitric acid KA oil is oxidized to hexanodioic acid then, this route accounts for global overall throughput about 93%.Its reaction process is as follows:
Second step of the first step
Industrial method by hexalin and Cyclohexanone Production hexanodioic acid is derived from E.I.Du Pont Company's eighties of last century the forties technology at present, be to prepare hexanodioic acid with 40-60% nitric acid and copper, vanadium catalyst catalyzed oxidation hexalin and pimelinketone under the 70-90 ℃ of temperature, reaction yield is 70-90%, reaction needs to use nitric acid, serious to equipment corrosion, and can produce the oxynitride that environment is had severe contamination.And the technological process of oxidizing ethyle alkyl production hexalin and pimelinketone is often used homogeneous cobalt catalyst based (ZL94110939.9), have the intermediate product cyclohexyl hydroperoxide to generate in the reaction process, product yield is low, and needs with a large amount of strong acid and strong base solution, etching apparatus, contaminate environment.In a word, more than utilize hexanaphthene to become KA oil transformation efficiency generally＜10% for cyclohexane oxidation in the two step production technique the first steps of raw material production hexanodioic acid, selectivity 70-90% produces a large amount of waste lyes; Produce the oxynitrides that environment is had severe contamination in the second step nitric acid oxidation process, serious to equipment corrosion, the operational condition harshness.Therefore, scientific and technical boundary is devoted to the research of hexanodioic acid new preparation process always.
In Chinese invention patent application CN 1714069A, Rhodia daiamid midbody Co.,Ltd discloses a kind of in the presence of lipophilic monocarboxylic acid solvent, use transition-metal catalyst (particularly manganese base and cobalt-base catalyst) that the hexanaphthene Catalytic Oxygen is changed into hexanodioic acid, and the hexanodioic acid that generates with water extraction, with the method for lipotropy non-polar solvent extract solvent carboxylic acid.Its catalyst component can be dissolved in reaction mixture with the form of compound and form homogeneous catalysis system, also can load, absorb or be attached to inert support (as silicon oxide or aluminum oxide) and go up and reaction mixture formation nonhomogeneous system.Being prepared by the hexanaphthene catalyzed oxidation has intermediate product cyclohexyl hydroperoxide and ester to generate simultaneously in the hexanodioic acid process, in order to improve yield, the said firm discloses the esterolytic method that use strong acid (as nitric acid, sulfuric acid) impels generation in Chinese patent CN 1714068A, disclose the method that promotes cyclohexylhydroperoxconversion conversion with acetylacetonate manganese in patent ZL 03809971.3.Integrate and see, this complex technical process need be through repeatedly reacting and separating, and required equipment is more, and investment is big, the cost height.
Chinese invention patent 95195040.1 discloses and has used cobalt acetate tetrahydrate catalyzer one to go on foot the route that is prepared hexanodioic acid by the hexanaphthene direct oxidation, but its catalyzer is a homogeneous catalyst, Separation and Recovery process complexity.In the Chinese invention patent application in the patent of CN1344240A and CN1308599A, RPC Inc. discloses the method that becomes separation and Extraction catalyzer the reaction mixture of hexanodioic acid from cyclohexane oxidation, this method is utilized extraction process separated salt catalyzer, and the use of special extraction cells has increased whole operational path cost.
In the patent of CN 101041615A, the method of a kind of schiff bases-porphyrin metallic compound catalyzed oxidation six-membered carbon ring compound (hexanaphthene, hexalin, pimelinketone or tetrahydrobenzene) is disclosed, the schiff bases-porphyrin metallic compound can also be immobilized on inorganic or organic high molecular compound in this method, for making co-catalyst, comprise hexanodioic acid with transition metal salt or oxide compound in the final product.
Chinese invention patent ZL200310110458.4, ZL03118249.6 and ZL200310110349.2 disclose the use metalloporphyrin and have made catalyzer, and air oxidation of cyclohexane prepares the method for hexanodioic acid.This method is the homogeneous catalysis process, the catalytic efficiency height, but metalloporphyrin type homogeneous catalyst is expensive, and can't reclaim and reuse.
ZL 99121017.4 discloses a kind of method of catalyzed oxidation tetrahydrobenzene synthesizing adipic acid, and this is invented with peroxide tungstate-organic carboxyl acid class co-ordination complex [W (O) (O
2)
2L
(2)]
2-Be catalyzer, under 66-92 ℃, use 30% hydrogen peroxide to be oxygenant, catalyzed oxidation tetrahydrobenzene synthesizing adipic acid.This technology is not with an organic solvent made reaction medium, does not use nitric acid yet, realized cleaner production, but oxygenant is dense hydrogen peroxide, and cost is higher.
Divided by hexanaphthene or tetrahydrobenzene is outside the raw material synthesizing adipic acid, adopting divinyl in addition is raw material, by hydro-carboxylation (US pat.5166421, US pat.3876695) or carbonyl alkoxide approach such as (USpat.4258203) prepare the technology of hexanodioic acid, these technology generally also are the homogeneous catalysis process.But, develop that a kind of to go on foot cyclohexane oxidation with air or oxygen one be the attention that the heterogeneous catalytic oxidation technology of hexanodioic acid is subjected to the investigator always because homogeneous catalysis oxidising process ubiquity catalyzer is difficult to the shortcoming of separating and reclaiming.Use heterogeneous solid catalyst can reduce aftertreatment costs such as product separation and purification by simple operations Separation and Recovery catalyzer such as centrifugal or filtrations.
[Angewate Chemie International Edition 2000 such as Dugal M, 39:2310] reported a kind of FeAlPO molecular sieve, can be used for the heterogeneous catalyst of oxidation step hexanaphthene to hexanodioic acid, used oxygenant is an air or oxygen, temperature of reaction is 100-130 ℃, and this activity of such catalysts is about 10～20mol (hexanaphthene) mol (Fe)
-1H
-1In recent years report RuO in the world
2Can be used as and have fine active oxide catalyst, activate molecular oxygen well can be used for the oxidizing reaction [Journal Of The American Chemical Society 2003,125:2195] of the alcohol under the mild conditions.[Canadian Journal Of Chemistry 2003,81:764] such as Zhan BZ will be wrapped in the RuO in the molecular sieve cage
2The catalyzed oxidation that is used for hexanaphthene, but primary product is pimelinketone and hexalin, and activity is about 10～20mol (hexanaphthene) mol (Ru)
-1H
-1The used oxygenant of this method is a tertbutyl peroxide, and its price is comparatively expensive, is unsuitable for industrial application.Up to the present, do not see that employing is with RuO
2Be the heterogeneous catalyst of active ingredient, utilize air or oxygen to be oxygenant, the open report of catalyzed oxidation hexanaphthene one step preparation adipic acid.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide that a kind of flow process is simple, the novel process of the catalyzed oxidation hexanaphthene one step preparation hexanodioic acid of environmental protection, safety.
The present invention is with highly active RuO
2Be the heterogeneous catalyst of active ingredient, utilize air or oxygen to be oxidizer catalytic oxidizing ethyle alkyl one step preparation hexanodioic acid.Specifically to be (1) prepare hexanodioic acid by hexanaphthene is a step catalytic oxidation, and route is short; (2) temperature of reaction and pressure are lower, are oxygenant with the air or oxygen, environmental pollution and the equipment corrosion of having avoided the use of nitric acid to cause; (3) use with RuO
2Be the solid catalyst of active ingredient, react and be heterogeneous catalysis process, catalytic activity height, catalyzer separate easily and recycling.Technology of the present invention compared with prior art, technical process is simple, environmental pollution and the equipment corrosion of having avoided the use of nitric acid to cause; Use heterogeneous catalyst to solve that catalyzer is difficult to recycle and the product separation problem in the homogeneous catalysis process; The reactive behavior height, good to the hexanodioic acid selectivity, can suppress the consecutive side reaction, reduce the generation of deep oxidation product.
The object of the present invention is achieved like this:
Hexanaphthene, solvent, initiator joined in the reactor with the solid catalyzer mix, form mixed suspension; The organic solvent of described solvent for mixing with hexanaphthene; Described catalyzer is the ru oxide of solid carrier load, solid carrier is aluminum oxide, molecular sieve, carbon nanotube, silicon-dioxide, activated carbon, zeolite, sepiolite, porous ceramics or polyvinyl chloride, and the mass ratio of solid carrier and ru oxide is for being 1-99: 1; Described initiator is selected from one or more in tertbutyl peroxide, butanone, hexalin, the pimelinketone; The weight ratio of described hexanaphthene and solvent is 1: 0-99, and the weight ratio of hexanaphthene and catalyzer is 10-8000: 1, the weight ratio of hexanaphthene and initiator is 1: 1-2000, described catalyst weight is the gross weight that comprises carrier;
(2) step (1) gained mixing suspension is warming up to 50-250 ℃, the oxygen of feeding sufficient quantity or air are as oxygenant, and reactor pressure is 0.1-5MPa, and the reaction times is 0.1-20h; Capacity is meant that the oxygenant that reaction process consumes can compensate by continuous aerating oxygen or air, to keep reactor pressure constant.
(3) step (2) reaction mixture is separated, obtain solid catalyst and the liquid mixture that contains reaction product, unreacted reactant and solvent;
(4) with after isolating hexanodioic acid in the isolated liquid phase mixture of step (3), the residue mother liquor mixes with reaction raw materials and turns back in the reactor.Contain hexanaphthene, hexalin, pimelinketone, Succinic Acid, pentanedioic acid, hexanodioic acid etc. in the isolated liquid phase mixture, can adopt general known method separation, the hexanodioic acid of purifying out.The solid catalyst that separation obtains can be reused and be used for next reaction cycle.
Describedly can be preferably acetone, methyl alcohol, ethanol, acetate or acetonitrile with the organic solvent that hexanaphthene mixes.
Described initiator is preferably hexalin, pimelinketone.
The weight ratio of described hexanaphthene and catalyzer is preferably 200-600: 1.
The temperature of reaction of described step (2) is preferably 100-200 ℃.
Described reaction pressure is preferably 0.5-2.5MPa.
The described reaction times is preferably 1-16h.
Technology of the present invention can adopt operate continuously, also can adopt the batch-type periodical operation.Isolated catalyzer, intact hexanaphthene and reaction product and the solvent etc. of unreacted can add former reaction unit, proceed reaction.
The ru oxide catalyzer of solid carrier load of the present invention is called in the preparation method's of carbon nanotube supported nanometer hydrated ruthenium oxide the patent (200610033782.4) open (publication number is CN1806914A) in the name that the applicant proposes, and its concrete preparation method comprises the steps:
(1) carbon nanotube is joined in the ruthenium trichloride solution, wherein carbon nanotube: ruthenium trichloride: the weight ratio of water is 1: 0.05～1: 20～200, sonic oscillation 0.5～4h;
(2) at room temperature, slowly drip hydrogen peroxide, the weight ratio of hydrogen peroxide and ruthenium trichloride is 100～600: 1, dropping time 2～10h;
(3) stir and be warmed up to 50～100 ℃, back flow reaction 2～6h;
(4) with suspension filtered, wash solid successively with distilled water, acetone, under 100～120 ℃, dry 8～24h makes carbon nanotube supported nanometer hydrated ruthenium oxide at last.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts the operational path of direct oxidation hexanaphthene one step preparation hexanodioic acid, reduced present industry in two steps reaction scheme cause with high investment, expensive, temperature of reaction of the present invention and pressure are lower, process is simple, easily realizes and controls;
(2) the present invention has avoided the nitric acid in the present hexanodioic acid industrial production to use, and has reduced the requirement to conversion unit, has avoided producing in the nitric acid oxidation process environmentally harmful oxynitride (NO, NO
2And N
2O) discharging;
(3) the present invention adopts the RuO of solid carrier load
2As catalyzer, to compare with the homogeneous catalyst that generally adopts at present, catalyzer separates with the product direct filtration, and simple to operate, catalyzer is reusable, saves the noble metal catalyst cost, reduces environmental pollution;
(4) RuO of the present invention's employing
2Catalyzer is compared with existing molecular sieve catalyst, and active high to the hexanaphthene catalytic oxidation, selectivity is good, has better catalytic effect, and reusable, has good stability.
Embodiment
The present invention is described further below in conjunction with embodiment, but protection scope of the present invention is not limited to the scope that embodiment represents.
Embodiment 1
The 237g hexanaphthene joined in the closed reaction kettle with solid catalyst with acetone, tertbutyl peroxide mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, and hexanaphthene and load have RuO
2The weight ratio of solid catalyst be 474: 1, catalyzer is the RuO of carbon nanotube carrier load
2, the publication number that is proposed by the applicant is the described preparation embodiment 1 method preparation of CN1806914A patent application, its solid carrier and RuO
2Weight ratio 90: 10.The weight ratio of hexanaphthene and tertbutyl peroxide is 34: 1.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen is to 1.5Mpa, because reaction process constantly consumes oxygen with stoichiometric ratio, so carry out in the process by the stable-pressure device and the continuous supplemental oxygen of under meter that link to each other with source of oxygen and keep-up pressure constant at 1.5Mpa in reaction.Reacted 8 hours, and, it filtered from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture, obtain solid catalyst and contain unreacted reactant and reaction product liquid phase mixture, this liquid phase mixture is analyzed to determine the transformation efficiency and the selectivity of reaction.Analytical procedure is carried out according to patent CN1936586A disclosed method, wherein the analysis of hexanaphthene, pimelinketone, hexalin is carried out on Agilent 6820 gas-chromatographies that capillary column is housed, and the analysis of hexanodioic acid, Succinic Acid, pentanedioic acid is carried out on Agilent 1100 liquid chromatographies.Reaction conversion ratio and as follows to the selectivity of hexanodioic acid.The separation of this liquid phase mixture and the purification of hexanodioic acid can be according to general known physics and chemical processes, adopt conventional decompress filter and recrystallization method in the present embodiment, can obtain purity and be 99.0% hexanodioic acid.
As shown in table 1, along with the increase in reaction times, conversion of cyclohexane and hexanodioic acid selectivity progressively increase, and after reaction 8 hours, conversion of cyclohexane is near 40%, and wherein the hexanodioic acid selectivity is greater than 65%.Calculate RuO
2The activity of such catalysts transformation frequency is 378mol (hexanaphthene) mol (Ru)
-1H
-1, the effect that obviously is better than all kinds of solid catalysts reported in the document (is generally 10～20mol (hexanaphthene) mol (active ingredient)
-1H
-1).Present embodiment utilizes RuO
2Catalyzer is an oxygenant with oxygen, under comparatively gentle condition the hexanaphthene oxidation step is become hexanodioic acid, the reactive activity height, and selectivity is good.Under up to 38.8% transformation efficiency, the product of degree of not meeting oxidation generates.Solid catalyst can separate easily to reuse.And present embodiment has been avoided pollution and the equipment corrosion of the use of nitric acid to environment.
Table 1
| Reaction times (hour) | Cyclohexane conversion | The hexalin selectivity | The pimelinketone selectivity | The Succinic Acid selectivity | The pentanedioic acid selectivity | The hexanodioic acid selectivity |
| 0.5 1.5 2.5 3.5 4.5 5.5 6.5 8 | 2.3％ 4.6％ 7.5％ 12.3％ 17.9％ 21.3％ 24.3％ 38.8％ | 49.7％ 39.7％ 29.7％ 22.7％ 18.1％ 16.3％ 14.1％ 10.3％ | 40.7％ 31.1％ 30.5％ 28.4％ 23.0％ 21.2％ 18.0％ 14.9％ | 0.0％ 0.4％ 0.7％ 0.8％ 0.6％ 0.2％ 0.8％ 1.3％ | 0.8％ 1.8％ 2.0％ 1.5％ 2.7％ 3.9％ 4.1％ 6.1％ | 8.8％ 27.0％ 37.1％ 46.6％ 55.8％ 58.4％ 63.0％ 67.4％ |
Embodiment 2～4
237g hexanaphthene and acetone, pimelinketone and solid catalyst joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, and hexanaphthene and load have RuO
2The weight ratio of solid catalyst be 474: 1, catalyzer is the RuO of carbon nanotube carrier load
2, the publication number that is proposed by the applicant is the described preparation embodiment 1 method preparation of CN1806914A patent application, its solid carrier and RuO
2Weight ratio 90: 10.The weight ratio of hexanaphthene and pimelinketone is 40: 1.Should under agitation be heated to the temperature shown in the table 2 respectively by mixed suspension, aerating oxygen is to 1.5Mpa, because reaction process constantly consumes oxygen with stoichiometric ratio, so carry out in the process by the stable-pressure device and the continuous supplemental oxygen of under meter that link to each other with source of oxygen and keep-up pressure constant at 1.5Mpa in reaction.Reacted 8 hours, and, it filtered from Polycondensation Reactor and Esterification Reactor relief liquor solid-phase mixture, obtain solid catalyst and contain unreacted reactant and reaction product liquid phase mixture, this liquid phase mixture is analyzed to determine the transformation efficiency and the selectivity of reaction.Analytical procedure is carried out according to patent CN1936586A disclosed method, wherein the analysis of hexanaphthene, pimelinketone, hexalin is carried out on Agilent 6820 gas-chromatographies that capillary column is housed, and the analysis of hexanodioic acid, Succinic Acid, pentanedioic acid is carried out on Agilent 1100 liquid chromatographies.Reaction conversion ratio and as follows to the selectivity of hexanodioic acid.The separation of this liquid phase mixture and the purification of hexanodioic acid can be according to general known physics and chemical processes, adopt conventional decompress filter and recrystallization method in the present embodiment, can obtain purity and be respectively 99.0%, 99.4%, 99.2% hexanodioic acid.
Embodiment 2～4 shows, according to method of the present invention, can realize the catalyzed oxidation of hexanaphthene under lower temperature, and the selectivity of hexanodioic acid is more excellent in the resulting product.As shown in table 2, when temperature of reaction was 125 and 250 ℃, reaction conversion ratio was higher.Wherein in the time of 125 ℃, can obtain more excellent hexanodioic acid selectivity, hexanodioic acid selectivity 71% under this temperature.Proved that method of the present invention is applicable to preparing adipic acid by using cyclohexane catalytic oxidation one-step under the gentle condition.
Table 2 temperature of reaction is to the influence of cyclohexane oxidation
| Embodiment | 2 | 3 | 4 |
| Temperature of reaction (℃) | 50 | 125 | 250 |
| Cyclohexane conversion | 4％ | 42％ | 57％ |
| The hexanodioic acid selectivity | 32％ | 71％ | 43％ |
Embodiment 5
The acetone of 237g hexanaphthene and respective amount, pimelinketone and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of solvent and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1, and catalyzer is the RuO of carbon nanotube carrier load
2, the publication number that is proposed by the applicant is the described preparation embodiment 1 method preparation of CN1806914A patent application, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 1MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 24%, and the hexanodioic acid selectivity is 38%.
Embodiment 6
The acetone of 237g hexanaphthene and respective amount, pimelinketone and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of solvent and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1, and catalyzer is the RuO of carbon nanotube carrier load
2, the publication number that is proposed by the applicant is the described preparation embodiment 1 method preparation of CN1806914A patent application, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 5MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 51%, and the hexanodioic acid selectivity is 69%.
Embodiment 7
The ethanol of 237g hexanaphthene and respective amount, tertbutyl peroxide and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of ethanol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1, and catalyzer is the RuO of alumina carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into aluminium sesquioxide, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation heat 125 ℃ by mixed suspension, aerating oxygen reacted 8 hours to certain pressure, and the separation of product and analytical procedure be with embodiment 1～4, reaction conversion ratio and selectivity such as following table 3.The raising reaction pressure helps the conversion of hexanaphthene, and transformation efficiency was higher when reaction pressure was 1.5MPa and 5MPa, and the selectivity of hexanodioic acid is best at 1.5MPa.
Table 3 reaction pressure is to the influence of cyclohexane oxidation
| Reaction pressure (Mpa) | 1.0 | 1.5 | 5.0 |
| Cyclohexane conversion | 16％ | 34％ | 48％ |
| The hexanodioic acid selectivity | 27％ | 62％ | 46％ |
Embodiment 8
The ethanol of 237g hexanaphthene and respective amount, tertbutyl peroxide and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of ethanol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1, and catalyzer is the RuO of alumina carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into aluminium sesquioxide, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to 50 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 2%, and the hexanodioic acid selectivity is 19%.
Embodiment 9
The ethanol of 237g hexanaphthene and respective amount, tertbutyl peroxide and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of ethanol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1, and catalyzer is the RuO of alumina carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into aluminium sesquioxide, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to 250 ℃ by mixed suspension, aerating oxygen reacted 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 45%, and the hexanodioic acid selectivity is 36%.
Embodiment 10
The acetonitrile of 5g hexanaphthene and respective amount, hexalin and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetonitrile and hexanaphthene is 99: 1, and the weight ratio of hexanaphthene and catalyzer is 10: 1, and the weight ratio of hexanaphthene and hexalin is 1: 1, and catalyzer is the RuO of molecular sieve carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into molecular sieve, its solid carrier and RuO
2Weight ratio 1: 1.Should under agitation be heated to 50 ℃ by mixed suspension, aerating oxygen is to 5MPa, and behind the reaction certain hour, the separation of product and analytical procedure be with embodiment 1～4, reaction conversion ratio and selectivity such as following table 4.The transformation efficiency of reaction and selectivity all increase with the reaction times, and it is favourable therefore selecting the suitably long reaction times.
Table 4 reaction times is to the influence of cyclohexane oxidation
| Reaction times (hour) | 0.1 | 8 | 20 |
| Cyclohexane conversion | 0.1％ | 4％ | 11％ |
| The hexanodioic acid selectivity | 4％ | 21％ | 39％ |
Embodiment 11
The acetonitrile of 395g hexanaphthene and respective amount, hexalin and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetonitrile and hexanaphthene is 0: 1, and the weight ratio of hexanaphthene and catalyzer is 8000: 1, and the weight ratio of hexanaphthene and hexalin is 2000: 1, and catalyzer is the RuO of molecular sieve carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into molecular sieve, its solid carrier and RuO
2Weight ratio 1: 1.Should under agitation be heated to 125 ℃ by mixed suspension, aerating oxygen reacts after 8 hours to 1.5MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 5%, and the hexanodioic acid selectivity is 24%.
Embodiment 12
The acetate of 350g hexanaphthene and respective amount, butanone and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetate and hexanaphthene is 1: 9, and the weight ratio of hexanaphthene and catalyzer is 50: 1, and the weight ratio of hexanaphthene and butanone is 99: 1, and catalyzer is the RuO of activity carbon carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into activated carbon, its solid carrier and RuO
2Weight ratio 99: 1.Should under agitation be heated to 250 ℃ by mixed suspension, aerating oxygen reacts after 8 hours to 5MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 7%, and the hexanodioic acid selectivity is 22%.
Embodiment 13
The acetate of 350g hexanaphthene and respective amount, butanone and solid catalyzer joined in the airtight batch reactor mix, form mixed suspension.Wherein, the weight ratio of acetate and hexanaphthene is 1: 9, and the weight ratio of hexanaphthene and catalyzer is 50: 1, and the weight ratio of hexanaphthene and butanone is 99: 1, and catalyzer is the RuO of activity carbon carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into activated carbon, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to 50 ℃ by mixed suspension, bubbling air reacts after 8 hours to 0.1MPa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 1%, and the hexanodioic acid selectivity is 12%.
Catalyst stability embodiment 1
(1) acetone of 237g hexanaphthene and respective amount, pimelinketone and solid catalyzer are joined in the airtight batch reactor and mix, form mixed suspension.Wherein, the weight ratio of acetone and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and pimelinketone is 40: 1, and catalyzer is the RuO of carbon nanotube carrier load
2, the publication number that is proposed by the applicant is the described preparation embodiment 1 method preparation of CN1806914A patent application, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation be heated to certain temperature by mixed suspension, aerating oxygen reacted 8 hours to 1.5Mpa, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 42%, and the hexanodioic acid selectivity is 71%
(2) with after the catalyzer filtered and recycled after having reacted in (1), by (1) described operation repeated experiments, product is analyzed, as shown in table 5, cyclohexane conversion is 41%, and the hexanodioic acid selectivity is 75%; Use to reclaim repeatedly catalyzer, the 3rd time the round-robin cyclohexane conversion is 39%, the hexanodioic acid selectivity is 76%, the 4th round-robin cyclohexane conversion is 42%, the hexanodioic acid selectivity is 73%.Employed RuO in the technology of the present invention is described
2Catalyzer can be recycled, and this helps reducing production costs.
The RuO that table 5 is carbon nanotube loaded
2The recycling of catalyzer
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency | 42％ | 41％ | 39％ | 42％ |
| Selectivity | 71％ | 75％ | 76％ | 73％ |
Catalyst stability embodiment 2
(1) ethanol of 237g hexanaphthene and respective amount, tertbutyl peroxide and solid catalyzer are joined in the airtight batch reactor and mix, form mixed suspension.Wherein, the weight ratio of ethanol and hexanaphthene is 1: 1.5, and the weight ratio of hexanaphthene and catalyzer is 474: 1, and the weight ratio of hexanaphthene and tertbutyl peroxide is 40: 1, and catalyzer is the RuO of alumina carrier load
2, the publication number that its preparation method and applicant propose is that described preparation embodiment 1 method of CN1806914A patent application is similar, only multi-walled carbon nano-tubes is replaced into aluminium sesquioxide, its solid carrier and RuO
2Weight ratio 90: 10.Should under agitation heat 125 ℃ by mixed suspension, aerating oxygen 1.5MPa reacted 8 hours, and the separation of product and analytical procedure are with embodiment 1～4, and cyclohexane conversion is 34%, and the hexanodioic acid selectivity is 62%;
(2) with after the catalyzer filtered and recycled after having reacted in (1), by (1) described operation repeated experiments, product is analyzed, as shown in table 6, cyclohexane conversion is 32%, and the hexanodioic acid selectivity is 64%; Use to reclaim repeatedly catalyzer, the 3rd time the round-robin cyclohexane conversion is 29%, the hexanodioic acid selectivity is 58%, the 4th round-robin cyclohexane conversion is 31%, the hexanodioic acid selectivity is 63%.Employed RuO in the technology of the present invention is described
2Catalyzer can be recycled, and this helps reducing production costs.
Table 6Al
2O
3The RuO of load
2The recycling of catalyzer
| Access times | 1 | 2 | 3 | 4 |
| Transformation efficiency | 34％ | 32％ | 29％ | 31％ |
| Selectivity | 62％ | 64％ | 58％ | 63％ |
Claims (6)
1, a kind of method of preparing adipic acid by using cyclohexane catalytic oxidation one-step is characterized in that comprising the steps:
(1) hexanaphthene, solvent, initiator are joined in the reactor with the solid catalyzer mixes, form mixed suspension; The organic solvent of described solvent for mixing with hexanaphthene; Described catalyzer is the ru oxide of solid carrier load, solid carrier is aluminum oxide, molecular sieve, carbon nanotube, silicon-dioxide, activated carbon, zeolite, sepiolite, porous ceramics or polyvinyl chloride, and the mass ratio of solid carrier and ru oxide is for being 1-99: 1; Described initiator is selected from one or more in tertbutyl peroxide, butanone, hexalin, the pimelinketone; The weight ratio of described hexanaphthene and solvent is 1: 0-99, and the weight ratio of hexanaphthene and catalyzer is 10-8000: 1, the weight ratio of hexanaphthene and initiator is 1: 1-2000, described catalyst weight is the gross weight that comprises carrier;
(2) step (1) gained mixing suspension is warming up to 50-250 ℃, the oxygen of feeding sufficient quantity or air are as oxygenant, and reactor pressure is 0.1-5MPa, and the reaction times is 0.1-20h;
(3) step (2) reaction mixture is separated, obtain solid catalyst and the liquid mixture that contains reaction product, unreacted reactant and solvent;
(4) with after isolating hexanodioic acid in the isolated liquid phase mixture of step (3), the residue mother liquor mixes with reaction raw materials and turns back in the reactor.
2,, it is characterized in that the described organic solvent that can mix with hexanaphthene is acetone, methyl alcohol, ethanol, acetate or acetonitrile according to the method for the described preparing adipic acid by using cyclohexane catalytic oxidation one-step of claim 1.
3, according to the method for the described preparing adipic acid by using cyclohexane catalytic oxidation one-step of claim 1, the weight ratio that it is characterized in that described hexanaphthene and catalyzer is 200-600: 1.
4,, it is characterized in that temperature of reaction 100-200 ℃ of described step (2) according to the method for the described preparing adipic acid by using cyclohexane catalytic oxidation one-step of claim 1.
5,, it is characterized in that described reactor pressure is 0.5-2.5MPa according to the method for the described preparing adipic acid by using cyclohexane catalytic oxidation one-step of claim 1.
6,, it is characterized in that described reaction times 1-16h according to the method for the described preparing adipic acid by using cyclohexane catalytic oxidation one-step of claim 1.
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| FR2722783B1 (en) * | 1994-07-21 | 1996-08-30 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF ADIPIC ACID BY DIRECT OXIDATION OF CYCLOHEXANE AND RECYCLING OF THE CATALYST |
| FR2828194B1 (en) * | 2001-08-03 | 2004-03-19 | Rhodia Polyamide Intermediates | PROCESS FOR THE OXIDATION OF ACID HYDROCARBONS |
| CN1218922C (en) * | 2003-04-08 | 2005-09-14 | 湖南大学 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
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