CN101773849A - Catalyst used for synthesizing cyclohexanol and cyclohexanone and preparation method thereof - Google Patents
Catalyst used for synthesizing cyclohexanol and cyclohexanone and preparation method thereof Download PDFInfo
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- CN101773849A CN101773849A CN201010022774A CN201010022774A CN101773849A CN 101773849 A CN101773849 A CN 101773849A CN 201010022774 A CN201010022774 A CN 201010022774A CN 201010022774 A CN201010022774 A CN 201010022774A CN 101773849 A CN101773849 A CN 101773849A
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Abstract
The invention discloses a catalyst used for synthesizing cyclohexanol and cyclohexanone (the mixture of the cyclohexanol and the cyclohexanone is commonly called as KA oil) by the catalytic oxidation of cyclohexane and a preparation method. The catalyst is an immobilized AlPO-5 molecular sieve catalyst containing copper and comprises an active component of Cu2+ and a carrier of an AlPO-5 molecular sieve. By adopting the catalyst, the reaction temperature is 140 DEG C, the reaction is carried out for 5h under the condition that the reaction pressure is 0.5MPa, the conversion rate of the cyclohexane reaches 8.2 percent, and the overall selectivity of the cyclohexanol and the cyclohexanone reaches 98 percent. The catalyst can be repeatedly used for many times without inactivation, has no pollution to the environment, is a simple, convenient, economical and environment-friendly catalyst for preparing the KA oil and provides probability for realizing industrialization in synthesizing the KA oil by the oxidation of the cyclohexane.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method who is used for the pure and mild cyclohexanone of cyclohexane catalytic oxidation synthesizing cyclohexane 1 (both mixtures are commonly called as KA oil), described catalyst is a kind of immobilized AlPO-5 molecular sieve catalyst of cupric.
Technical background
The partial oxidation of alkane is one of research topic of the challenging meaning in current catalytic chemistry field.This is reflected on the Chemical Manufacture also significant.Wherein, the cyclohexane catalytic oxidation is a noticeable goal response.The whole world approximately can produce 106 tons of cyclohexanol and cyclohexanone every year, is mainly used in the production adipic acid, and then produces nylon 6 and nylon 66.At present used oxidation catalyst is undesirable, and people are seeking a kind of have high selectivity, high stability and eco-friendly cyclohexane oxidation catalyst.
The industrial method of synthesizing and prepare KA oil mainly contains phenol hydrogenation method, benzene hydrogenation method, cyclohexane oxidation process, and wherein the application of cyclohexane oxidation process is the most general.
Phenol is through catalytic hydrogenation system cyclohexanol, the dehydrogenation technology of producing cyclohexanone starts from the 1950's again, but this technology coproduction accessory substance acetone, and benzene needs just can make cyclohexanone through intermediate products such as isopropylbenzene, isopropyl benzene hydroperoxide, phenol, reactions steps is many, and the application of this technology is restricted.
Traditional benzene hydrogenation method is made cyclohexane by benzene hydrogenation, again catalytic oxidation system cyclohexanol and cyclohexanone.Cyclohexane is under 160～170 ℃, 0.81～1.22MPa condition, with cobalt naphthenate or boric acid is catalyst oxidation system cyclohexanol and cyclohexanone, this technology is in the industrialization sixties of 20th century, yet because cyclohexane conversion per pass low (＜10%), circulating consumption is big, is considered to a nonideal technology all the time.
The method that cyclohexane oxidation prepares cyclohexanol and cyclohexanone can be divided into non-catalytic oxidation method and catalytic oxidation.Difference according to oxidant in the cyclohexane oxidation can be divided into oxygen method and other oxidant method again.In the process of cyclohexane oxidation preparing cyclohexanone and cyclohexanol, oxidant is generally oxygen-containing gas (as air), pure oxygen, removes to also have H in addition
2O
2, Me
3COOH etc.The catalyst that adopts in the cyclohexane catalytic oxidation is generally the VIIB in the periodic table, VIIIB and I B family metal, and as Fe, Ru, Co, Mn, Cu etc., normally these metals and organic complex.Conversion of cyclohexane is very low, and condition is relatively harsher mostly.
Produce the traditional handicraft of cyclohexanol and cyclohexanone, cyclohexane conversion, alcohol ketone selectivity are all lower, complex process, and seriously polluted, therefore, the producer is constantly being improved it.The exploitation of catalyst and research become improved emphasis, have studied multiple catalyst system up till now, in the selectivity of conversion rate of oxidation that has improved cyclohexane in varying degrees and alcohol ketone.
Hetero-atom molecular-sieve---in cyclohexane catalytic oxidation preparing cyclohexanone, hetero-atom molecular-sieve becomes the focus of domestic and international many worker's researchs at present, and the molecular sieve of metals such as Co, Cr, Fe, V, Mn and Ti has good selective oxidation performance in this reaction.As Dapurkar (Journal ofMolecular Catalysis A:Chemical.2004,223:241～250) etc. with H
2O
2Be oxidant, the VMCM-41 molecular sieve property selected oxidizing ethyle alkyl, cyclohexane conversion reaches more than 90.0%, and the selectivity of alcohol ketone also reaches 96.4%; Reach 83.1% with the dioxygen oxidation conversion of cyclohexane, the alcohol ketone selectivity is greater than 95.3%; With the air is oxygen source, and cyclohexane conversion is 48.8%, and selectivity is higher than 98.3%; With TBHP (TBHP) is oxygen source, and cyclohexane conversion is 63.4%, and the alcohol ketone selectivity is greater than 82.4%.The VMCM-41 molecular sieve has high conversion and selectivity in this reaction, but cyclohexane produces H in oxidizing process
2O can have a negative impact to the unsettled VMCM-41 molecular sieve catalytic of hydro-thermal performance.Therefore, other scholars study other molecular sieves, (Catalysis Today.2004.93 (95): 735～742) studied Co, Cr, V, Mn, phosphorus aluminium series molecular sieve catalytic performance in this reaction such as Tian for example, the result shows that its cyclohexane conversion and alcohol ketone selectivity ratios VMCM-41 molecular sieve are low.Hetero-atom molecular-sieve have high selectivity and conversion ratio, but its reaction mechanism it be unclear that in cyclohexane selective oxidation system hexamethylene cyclohexanol and cyclohexanone reaction.Therefore, to develop more suitable catalyst be one of emphasis of current research work for the cyclohexane catalytic oxidation prepares cyclohexanol and cyclohexanone.
Summary of the invention
The objective of the invention is to overcome the synthetic KA oil of tradition a kind of high performance catalyst and preparation method are provided with the many disadvantages of catalyst.
Catalyst involved in the present invention is the immobilized AlPO-5 molecular sieve catalyst of cupric, by active component Cu
2+Constitute with carrier A lPO-5, wherein Cu
2+Shared ratio is 0.2～10% by weight in catalyst.
Catalyst of the present invention adopts the hydrothermal synthesis method preparation, and preparation process may further comprise the steps:
(a) deionized water, phosphoric acid and copper source are mixed; Triethylamine (TEA) is dropwise joined in the above-mentioned mixed solution, system presents muddiness again; Under stirring at room, aluminium isopropoxide (being called for short IPA1) is joined in the above-mentioned solution at leisure, at room temperature stir half an hour again after adding.
(b) above-mentioned material is added in the teflon-lined stainless steel cauldron, in crystallization under the specific crystallization temperature after a period of time, isolated by filtration and spend deionised water three times after drying, grinding, the roasting, has obtained Cu immobilized
2+The AlPO-5 molecular sieve catalyst;
The mol ratio of said above-mentioned each material is: H
3PO
4: 1.1TEA: xIPAl: yH
2O, (wherein x=1.0～2.0, y=50～100);
The copper source can be a soluble copper salt, preferred copper nitrate and copper sulphate, as: Cu (NO
3)
23H
2O, CuSO
45H
2O or the like;
Said crystallization temperature is 100～220 ℃, and crystallization time is 2～72h;
Drying condition is room temperature～160 ℃, vacuum, or the combination of above several modes; Sintering temperature is 300～700 ℃, and roasting time is 2～20h.
Technical essential of the present invention is to make active component immobilized by the copper-containing active component is doped in the AlPO-5 framework of molecular sieve, the catalytic oxidation rear catalyst can separate rapidly with reactant liquor, catalyst can reuse, reaction conversion ratio is higher, good product selectivity, the product purity height, environmentally safe.Compare with catalyst used during traditional KA oil is synthetic, the present invention has following several advantage: (1) catalyst can reuse; (2) cyclohexane oxidation reaction one step of preparing KA oil finishes, and preparation process is simple.Catalyst do not dissolve with reactant liquor in, can separate rapidly after reaction finishes, thereby improve the purity of product; (3) the reactant conversion of cyclohexane can reach 8.2%, and the cyclohexanone selectivity can reach 53%, and the cyclohexanol of generation and the overall selectivity of cyclohexanone can reach 98%.Compare with the conventional oxidation agent hydrogen peroxide, the present invention with oxygen is oxidant, and is more cheap, and catalyst can reuse, and whole reaction system is carried out under condition of no solvent, environmentally safe.Thereby this catalyst is a kind of economy, eco-friendly catalyst, for realizing that industrialization provides possibility.
The specific embodiment
Activity of such catalysts adopts method described below to estimate: cyclohexane, catalyst and initator hydrogen peroxide are joined in the 50mL autoclave, the back aerating oxygen that stirs keeps reaction pressure 0.5MPa, catalyst amount is every milliliter of cyclohexane 0.033g, obtains product at 110～160 ℃ of reaction 1～6h.
Embodiment 1
The synthetic immobilized Cu of hydro-thermal coprecipitation
2+The AlPO-5 molecular sieve catalyst:
(a) 7.85g water is mixed mutually with 1.01g phosphoric acid; Cu (NO with 0.032g
3)
23H
2O stirs as the copper source system that joins; 0.989g triethylamine (TEA) is added in the above-mentioned mixed solution, under stirring at room, the 1.78g aluminium isopropoxide is joined in the above-mentioned solution at leisure, at room temperature stir half an hour again after adding.
(b) above-mentioned material is added in the 50mL teflon-lined reactor, behind 120 ℃ of following crystallization 4h, isolated by filtration is again with 100mL deionized water washing three times, in 100 ℃ of baking ovens, spend the night, drying finish the back in air 500 ℃ of roasting 5h, obtain the 1# catalyst, catalyst performance evaluation the results are shown in Table 1.
Embodiment 2
With the Cu (NO among the embodiment 1
3)
23H
2The O consumption changes 0.064g into, and other processes obtain the 2# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 3
With the Cu (NO among the embodiment 1
3)
23H
2The O consumption changes 0.128g into, and other processes obtain the 3# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 4
Change the aluminium isopropoxide consumption among the embodiment 1 into 3.37g, other processes obtain the 4# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 5
Change the water consumption among the embodiment 1 into 14.1g, other processes obtain the 5# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 6
Change the crystallization temperature among the embodiment 1 into 100 ℃, other processes obtain the 6# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 7
Change the crystallization time among the embodiment 1 into 2h, other processes obtain the 7# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 8
Drying condition among the embodiment 1 changed under 120 ℃ vacuumize, other processes obtain the 8# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 9
Change the sintering temperature among the embodiment 1 into 700 ℃, other processes obtain the 9# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
Embodiment 10
Change the roasting time among the embodiment 1 into 2h, other processes obtain the 10# catalyst with embodiment 1, and catalyst performance evaluation the results are shown in Table 1.
The cyclohexane oxidation performance of each catalyst of table 1
Annotate: reaction condition: catalyst 0.5g, cyclohexane 10g, 0.5MPa oxygen, initator hydrogen peroxide 0.03g, 140 ℃ of reaction 5h.
Embodiment 11-16
The influence of reaction time to reacting: experiment condition is 1# catalyst 0.5g, cyclohexane 10g, and 0.5MPa oxygen, initator hydrogen peroxide 0.03g, 140 ℃ of reaction 1-6h, embodiment 11-16 comparing result sees Table 2.
Table 2 reaction time is to the influence of reaction
Embodiment 17-22
The influence of reaction temperature to reacting: experiment condition is 1# catalyst 0.5g, cyclohexane 10g, 0.5MPa oxygen, initator hydrogen peroxide 0.03g, reaction 5h, reaction temperature is 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, embodiment 17-22 comparing result sees Table 3.
Table 3 reaction temperature is to the influence of reaction
Claims (7)
1. a catalyst that is used for the pure and mild cyclohexanone of cyclohexane catalytic oxidation synthesizing cyclohexane 1 (both mixtures are commonly called as KA oil) is characterized in that, a kind of immobilized AlPO-5 molecular sieve catalyst of cupric is by comprising catalyst activity component Cu
2+Constitute with carrier A lPO-5 molecular sieve.
2. according to the described catalyst of claim 1, it is characterized in that adopting the hydrothermal synthesis method preparation, preparation process may further comprise the steps:
(a) deionized water, phosphoric acid and copper source are mixed; Again triethylamine (being called for short TEA) is joined in the above-mentioned mixed solution, under stirring at room, aluminium isopropoxide (being called for short IPAl) is joined in the above-mentioned solution at leisure, at room temperature stir half an hour again after adding.
(b) above-mentioned material is added in the teflon-lined reactor, after a period of time, isolated by filtration spends deionised water three times again in crystallization under the specific crystallization temperature, after drying, grinding, the roasting, has obtained Cu immobilized
2+The AlPO-5 molecular sieve catalyst.
3. according to the described Preparation of catalysts method of claim 2, it is characterized in that the mol ratio of described each material is: H
3PO
4: 1.1TEA: xIPAl: yH
2O, (wherein x=1.0～2.0, y=50～100).
4. according to the described Preparation of catalysts method of claim 2, it is characterized in that described immobilized Cu
2+The AlPO-5 molecular sieve catalyst be to be the copper source with the soluble copper salt, preferred copper nitrate and copper sulphate, wherein, Cu
2+Shared ratio is 0.2～10% by weight in catalyst.
5. according to the described Preparation of catalysts method of claim 2, it is characterized in that described crystallization temperature is 100～220 ℃, crystallization time is 2～72h.
6. according to the described Preparation of catalysts method of claim 2, it is characterized in that drying condition is room temperature～160 ℃, or under room temperature～120 ℃, vacuumize; Sintering temperature is 300～700 ℃, and roasting time is 2～20h.
7. the process conditions of the pure and mild cyclohexanone of cyclohexane catalytic oxidation synthesizing cyclohexane 1, it is characterized in that, cyclohexane, catalyst and initator hydrogen peroxide are joined in the autoclave, the back aerating oxygen that stirs keeps reaction pressure 0.5MPa, catalyst amount is every milliliter of cyclohexane 0.033g, obtains product at 110～160 ℃ of reaction 1～6h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701905A (en) * | 2012-05-04 | 2012-10-03 | 华东理工大学 | Process for preparing cyclohexanone and cyclohexanol by cyclohexane selective oxidation |
| CN102921456A (en) * | 2012-11-07 | 2013-02-13 | 中国科学院上海硅酸盐研究所 | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst |
| CN104525183A (en) * | 2014-12-08 | 2015-04-22 | 太原理工大学 | Chromium base-loaded mesoporous catalyst and its preparation method and use |
| CN106179503A (en) * | 2016-07-08 | 2016-12-07 | 南京工程学院 | The catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene |
| CN109248699A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | The method of cyclohexane oxidation KA oil |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN112961048A (en) * | 2021-02-08 | 2021-06-15 | 中国石油大学(华东) | Technological method for co-producing K.A. oil and adipic acid by one-step method |
-
2010
- 2010-01-14 CN CN201010022774A patent/CN101773849A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701905A (en) * | 2012-05-04 | 2012-10-03 | 华东理工大学 | Process for preparing cyclohexanone and cyclohexanol by cyclohexane selective oxidation |
| CN102701905B (en) * | 2012-05-04 | 2015-03-18 | 华东理工大学 | Process for preparing cyclohexanone and cyclohexanol by cyclohexane selective oxidation |
| CN102921456A (en) * | 2012-11-07 | 2013-02-13 | 中国科学院上海硅酸盐研究所 | Heterogeneous catalyst, preparation method of heterogeneous catalyst and application of heterogeneous catalyst |
| CN104525183A (en) * | 2014-12-08 | 2015-04-22 | 太原理工大学 | Chromium base-loaded mesoporous catalyst and its preparation method and use |
| CN104525183B (en) * | 2014-12-08 | 2016-08-17 | 太原理工大学 | A kind of mesoporous catalyst loading chromio and its preparation method and application |
| CN106179503A (en) * | 2016-07-08 | 2016-12-07 | 南京工程学院 | The catalyst of hexamethylene height selective catalytic oxidation synthesizing cyclohexanol/Ketohexamethylene |
| CN109248699A (en) * | 2017-07-14 | 2019-01-22 | 中国石油化工股份有限公司 | The method of cyclohexane oxidation KA oil |
| CN109248699B (en) * | 2017-07-14 | 2022-08-12 | 中国石油化工股份有限公司 | Method for preparing KA oil by cyclohexane oxidation |
| CN111153831A (en) * | 2020-02-19 | 2020-05-15 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN111153831B (en) * | 2020-02-19 | 2022-11-01 | 湘潭大学 | Preparation method of cyclohexanone oxime |
| CN112961048A (en) * | 2021-02-08 | 2021-06-15 | 中国石油大学(华东) | Technological method for co-producing K.A. oil and adipic acid by one-step method |
| CN112961048B (en) * | 2021-02-08 | 2022-10-18 | 中国石油大学(华东) | Technological method for co-producing K.A. oil and adipic acid by one-step method |
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Open date: 20100714 |