CN101204664B - Multiphase catalytic oxidation cyclohexane catalyst for cyclohexanone and cyclohexanol and preparation method thereof - Google Patents
Multiphase catalytic oxidation cyclohexane catalyst for cyclohexanone and cyclohexanol and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heterogeneous catalysis used for preparing cyclohexanone and cyclohexanol by catalytic oxidation of cyclonexane and a preparation method thereof. The technical process thereof is that: according to a certain proportion, a carrier is mixed with a certain proportion of active metal nitrate solution. The carrier is aluminosilicate molecular sieve or silicon dioxide. The active metal is one or more transition metal element of IVB-VIIIB Group. The mixture is stirred for 1 to 3 hours at room temperature and then treated with standing impregnation for 5 to 12 hours, or stirred back flow at boiling temperature for 5 to 8 hours. The catalyst with active metal is obtained by that a supernatant is removed and a filter cake is dried at 80 to 120 DEG C, baked at 400 to 600 DEGC for 2 to 6 hours. The catalyst of the invention has the advantages of low price, gentle reaction condition, and high conversion efficiency of cyclonexane; cyclohexanol and cyclohexanone are with good selectivity; no carbon dioxide or black oil is generated from the reaction process; the catalyst is easily separated from reaction system after reaction.
Description
Technical field
The present invention relates to a kind of heterogeneous catalyst that is used for cyclohexane oxidation preparing cyclohexanone and cyclohexanol process and preparation method thereof.
Background technology
Cyclohexane oxidation preparing cyclohexanone and cyclohexanol (being called for short KA oil) are the important representatives of alkane oxidation course of industrialization, and its oxidation product cyclohexanone is mainly as producing nylon-6 and the raw material caprolactam of nylon-66 and the intermediate of adipic acid.Simultaneously KA oil also is important industrial solvent, and uses at industrial process such as resin, polyurethane foam plastics, medicine, paint, coating, rubber, plasticizer, agricultural chemicals, quality lubricant, binder, synthetic leather, synthetic dyestuffs, spices, yeast purification and having very widely aspect printing and the plastics recovery.
At present, the industrial manufacture process of cyclohexanone, cyclohexanol mainly contains three kinds in the world, that is: phenol hydrogenation, cyclohexane liquid-phase oxidation and cyclohexene hydration method, the wherein production of 90% KA oil employing cyclohexane oxidation process.And the industrialized technology of cyclohexane oxidation process can be divided into two kinds of on-catalytic and catalysis methods.The representative processes of on-catalytic method is the DSM/HPO process of Dutch DSM N. V. exploitation, and the whole world has 3,500,000 tons KA oil to produce by this technology every year approximately, also mainly is to adopt this kind technology in China.The key step of this technology is: cyclohexane is oxidized to cyclohexyl hydroperoxide (CHHP) by air (oxygen) under 130-150 ℃ and 0.8-1.2MPa condition, CHHP is cyclohexanol and cyclohexanone by NaOH/cobalt acetate catalyst decomposes under 65-85 ℃ and 0.1-0.3MPa condition; About 6 hours of entire reaction course, cyclohexane conversion 3-4%, cyclohexanol and cyclohexanone selectivity about 80%.The major defect of this technology is that process route complexity, intermediate steps are many, the cyclohexane conversion per pass is low, cyclohexanol and the cyclohexanone selectivity is not high, reagent has corrosivity, supplies consumption height and spent lye are difficult to handle etc.The cyclohexane oxidation system cyclohexanol of reporting in the patent and the catalyst of cyclohexanone mainly are homogeneous catalysts.Japan Patent JP63222132A2 report uses boric acid catalyst, cyclohexane conversion 3.6%, KA oil selectivity 91.6%.But such catalyst exists problems such as the higher and equipment corrosion of cost is serious.Japan your (Daicel) chemical industrial company of contest has developed acetylacetonate cobalt and N-hydroxyphthalimide mixture catalyzer (WO2000048975A1,2000-08-24; JP2000239210A2,2000-09-05), this catalyst system and catalyzing is oxidant with the air, under 160 ℃ and 4.0MPa condition, through reaction in 4 hours, cyclohexane conversion 11%, KA oil selectivity 89%.But such catalyst large usage quantity in technology, and cost an arm and a leg, the separating technology of mixture of reaction products is very complicated.Chinese patent 02139709.0 report uses the catalysis of metalloporphyrin agent, the air of 0.8MPa as the oxidant condition under, 135 ℃ of reactions 3 hours, conversion of cyclohexane 12.5%, KA oil selectivity 92%.But such catalyst performance instability, the synthetic difficulty of catalyst, and price is higher.Adopt homogeneous catalyst to carry out cyclohexane oxidation system KA oil, ubiquitous problem is, reaction finishes rear catalyst and reactant mixture and is difficult to separate and recycles, produce the dirty oil of thickness and the reactor obstruction and the residual catalyst that bring thus influence a series of problems such as downstream process.Also some patent reports have been arranged and be used for the heterogeneous catalyst of cyclohexane oxidation system KA oil.Chinese patent 200510017013.0 adopts the cupric pyrophosphate of polytetrafluoroethylene (PTFE) modified as catalyst, reaction is 5 hours under the condition of 150 ℃ of 1.3MPa oxygen and reaction temperatures, the yield of cyclohexanone and cyclohexanone is 6.31%, cyclohexene, cyclohexanol and cyclohexanone overall selectivity are 92.3%, and wherein cyclohexene accounts for 1.5%; World patent WO 2004071998-A2 adopts Au/ total silicon ZSM-5 catalyst to carry out cyclohexane oxidation, 170 ℃ of reaction temperatures, pressure 0.88-0.95MPa is under solvent-free condition, KA oil and cyclohexyl hydroperoxide selectivity 91.4%, cyclohexane conversion is 3.39%; U.S. Pat 20040158103 report, the TS-1 molecular sieve that adopts the Au load be as catalyst, is under 130-140psig and the 150 ℃ of thermotonus conditions in air pressure, conversion of cyclohexane 6-7%, KA oil selectivity 90%.But therefore this class catalyst costs an arm and a leg owing to used precious metal element, has limited its industrial applications.
Summary of the invention
The objective of the invention is to, defective at the prior art existence, a kind of heterogeneous catalyst that the cyclohexane catalytic oxidation is produced cyclohexanone and cyclohexanol that is used for is proposed, use this catalyst and under certain process conditions, carry out cyclohexane oxidation system cyclohexanol and cyclohexanone reaction, cyclohexane conversion reaches as high as 13.02%, and cyclohexanol and cyclohexanone selectivity can reach 80.43%.
One of technical scheme of the present invention is, the described cyclohexane catalytic oxidation that is used for is produced the heterogeneous catalyst of cyclohexanone and cyclohexanol and is made up of carrier and active metal component, and its technical characterictic is,
(1) described carrier is one of following two kinds:
A. aluminosilicate molecular sieves has the pore passage structure of 8 Yuans rings or 10 Yuans rings, 12 Yuans rings, and its framework si-al ratio is 5-100;
B. silica, granularity is the 200-600 order;
(2) described active metal component is one or more the arbitrary proportion combination in the IVB-VIIIB group 4 transition metal element, and the weight ratio content of this active metal component in catalyst that is incorporated on the described carrier by ion-exchange or dipping approach is 1%-12%.
Two of technical scheme of the present invention is, the described cyclohexane catalytic oxidation that is used for is produced the heterogeneous catalyst preparation method's of cyclohexanone and cyclohexanol processing step and is:
(1) be 15 by the reactive metal salting liquid with the weight ratio of carrier: 1-25 is that the reactive metal nitrate solution of 0.01mol/L-0.15mol/L mixes with described carrier and concentration, mixed liquor; Described carrier is one of following two kinds:
A. aluminosilicate molecular sieves has the pore passage structure of 8 Yuans rings or 10 Yuans rings, 12 Yuans rings, and its framework si-al ratio is 5-100;
B. silica, granularity is the 200-600 order;
Described reactive metal is one or more in the IVB-VIIIB group 4 transition metal element;
(2) mixed liquor was at room temperature stirred 1-3 hour, leave standstill impregnation process 5-12 hour again, or under boiling temperature stirring and refluxing 5-8 hour;
(3) remove supernatant liquor, filter cake is dried down at 80-120 ℃,
(4), time 2-6 hour, promptly obtain containing the catalyst of reactive metal in 400 ℃ of-600 ℃ of roasting temperatures.
Further, the catalyst that above-mentioned gained is contained reactive metal mixes with corresponding reactive metal nitrate solution in identical (solid-liquid) ratio of described step (1), and repeating step (2) to (4) 2-3 time obtains having the catalyst of different activities tenor.
Among the present invention, preferred catalyst carrier is the molecular sieve with MFI (orthorhombic system) structure of 10 Yuans annular distance road structures, and its silica alumina ratio scope preferably is 5-100, preferably 20-60.
The reactive metal that is adopted is one or more any combination in the IVB-VIIIB group 4 transition metal element, preferably a kind of the or any two kinds arbitrary proportion combination among Fe, Cu, Co, Mn, Cr, Mo, V, Ti, the W.
In the prepared catalyst, the weight ratio content of reactive metal is reasonable to be 1-12%, preferably 3-5%.
Catalyst of the present invention is used for cyclohexane oxidation system cyclohexanol and the cyclohexanone reaction is carried out at tank reactor; Reaction is solvent with acetic acid, and butanone is an initator, oxygen oxidizer, reaction temperature 110-150 ℃, preferred 120-140 ℃; Reaction pressure 0.5-1.2MPa, preferred 0.7-0.9MPa; Reaction time 2-8 hour, preferred 4-6 hour; Cyclohexane conversion reaches as high as 13.02%, and cyclohexanol and cyclohexanone selectivity can reach 80.43%.
As known from the above, the present invention is used for the cyclohexane catalytic oxidation to produce heterogeneous catalyst of cyclohexanone and cyclohexanol and preparation method thereof, its outstanding advantage is, catalyst is cheap, reaction condition is gentle, cyclohexane conversion is high, does not produce carbon dioxide and dirty oil, reaction end rear catalyst and reaction system convenient separation in cyclohexanol and cyclohexanone selectivity height, the course of reaction.
The specific embodiment
Embodiment 1: ZSM-5 (silica alumina ratio the is 50) powder that takes by weighing 2g joins in the copper nitrate solution that 40ml concentration is 0.1mol/L, at room temperature stirred 3 hours, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of down oven dry, and then is put in the high temperature stove 400 ℃ of roastings 2.5 hours.Make Cu content and be 2.1% Cu-ZSM-5.
The cyclohexane that in the tank reactor of 50ml, adds 10ml, the acetic acid of 10ml, the butanone of 1ml, and the Cu-ZSM-5 catalyst of the above-mentioned preparation of 0.02g.Feed molecular oxygen and make pressure remain on 0.85MPa, reaction temperature is 130 ℃, and the reaction time is 5 hours.Reaction result: cyclohexane conversion 4.88%, the selectivity of cyclohexanone are 56.10%, and the selectivity of cyclohexanol is 9.60%, and all the other are acetic acid hexamethylene alcohol ester, do not have carbon dioxide and dirty oil to produce.
Embodiment 2: ZSM-5 (silica alumina ratio the is 50) powder that takes by weighing 2g joins in the cobalt nitrate solution that 40ml concentration is 0.05mol/L, at room temperature stirred 3 hours, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of down oven dry, and then is put in the high temperature stove 400 ℃ of roastings 2.5 hours.Make Co content and be 1.8% Co-ZSM-5.
The cyclohexane that in the tank reactor of 50ml, adds 10ml, the acetic acid of 10ml, the butanone of 1ml, and the Co-ZSM-5 catalyst of the above-mentioned preparation of 0.02g.Feed molecular oxygen and make pressure remain on 1.2MPa, reaction temperature is 110 ℃, and the reaction time is 10 hours.Reaction result: cyclohexane conversion 4.23%, the selectivity of cyclohexanone are 59.40%, and the selectivity of cyclohexanol is 9.42%, and all the other are acetic acid hexamethylene alcohol ester, do not have carbon dioxide and dirty oil to produce.
Embodiment 3: ZSM-5 (silica alumina ratio the is 50) powder that takes by weighing 2g joins in the iron nitrate solution that 40ml concentration is 0.1mol/L, be placed under the room temperature and stirred 3 hours, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of down oven dry, and then is put in the high temperature stove 400 ℃ of roastings 2.5 hours.With gained Fe-ZSM-5 is starting material, adds iron nitrate solution, by aforesaid condition and step, repeats preparation procedure once, makes Fe content and be 1.9% Fe-ZSM-5.
The cyclohexane that in the tank reactor of 50ml, adds 10ml, the acetic acid of 10ml, the butanone of 1ml, and the Fe-ZSM-5 catalyst of the above-mentioned preparation of 0.02g.Feed molecular oxygen and make pressure remain on 0.5MPa, reaction temperature is 150 ℃, and the reaction time is 5 hours.。Reaction result is as follows: cyclohexane conversion is 2.55%, and the selectivity of cyclohexanone is 27.50%, and the selectivity of cyclohexanol is 24.59%, and remaining is an acetic acid hexamethylene alcohol ester, does not have carbon dioxide and dirty oil to produce.
Embodiment 4: ZSM-5 (silica alumina ratio the is 50) powder that takes by weighing 2g joins in the copper nitrate solution that 40ml concentration is 0.1mol/L, be placed under the room temperature and stirred 3 hours, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of down oven dry, and then is put in the high temperature stove 400 ℃ of roastings 2.5 hours.With gained Cu-ZSM-5 is starting material, adds copper nitrate solution, by aforesaid condition and step, repeats the preparation procedure secondary, makes Cu content and be 3.5% Cu-ZSM-5.
Reaction condition is identical with embodiment 1.Reaction result is as follows: cyclohexane conversion is 6.20%, and the selectivity of cyclohexanone is 50.70%, and the selectivity of cyclohexanol is 13.60%, and remaining is an acetic acid hexamethylene alcohol ester, does not have carbon dioxide and dirty oil to produce.
Embodiment 5: the mixed solution that ZSM-5 (silica alumina ratio the is 50) powder that takes by weighing 2g joins the cobalt nitrate of 40ml and copper nitrate (wherein, the concentration of cobalt nitrate and copper nitrate is respectively 0.1mol/L and 0.05mol/L) in, be placed under the room temperature and stirred 3 hours, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of down oven dry, and then is put in the high temperature stove 400 ℃ of roastings 2.5 hours.With gained Co-Cu-ZSM-5 is starting material, adds the solution that contains cobalt nitrate and copper nitrate, by aforesaid condition and step, repeats the preparation procedure secondary, and the content that makes Co and Cu is respectively 5.2% and 2.7% Co-Cu-ZSM-5.
Reaction condition is identical with embodiment 1.Reaction result is as follows: cyclohexane conversion is 6.35%, and the selectivity of cyclohexanone is 56.52%, and the selectivity of cyclohexanol is 10.50%, and remaining is an acetic acid hexamethylene alcohol ester, does not have carbon dioxide and dirty oil to produce.
Embodiment 6: make CATALYST Co-Cu-ZSM-5 as embodiment 4, reaction condition is identical with embodiment 1, respectively the product behind reaction 1h, 2h, 4h, 6h, 8h, 10h, the 12h is detected, and the result is as shown in table 1.
Table 1 time is to the result that influences of reaction
Reaction system: cyclohexane is 10ml, and acetic acid is 10ml, and butanone is 1ml; Reaction condition: 130 ℃ of temperature, pressure 0.85MPa,
Embodiment 7: with silica alumina ratio is that 100 ZSM-5 is a starting material, adopts condition and the program identical with embodiment 4, makes CATALYST Co-Cu-ZSM-5.Reaction condition is according to embodiment 1, and the reaction time is 8h.Reaction result is as follows: conversion of cyclohexane is 10.87%, and the selectivity of cyclohexanone is 43.27%, and the selectivity of cyclohexanol is 29.97%, and the selectivity of acetic acid hexamethylene alcohol ester is 26.76%, does not have carbon dioxide and dirty oil to produce.
Embodiment 8: with silica alumina ratio is that 75 modenite is a starting material, adopts condition and the program identical with embodiment 4, makes the Co-Cu-mordenite catalyst, and wherein, Co and the Cu content in catalyst is respectively 4.8% and 2.2%.Reaction condition is according to embodiment 1, and the reaction time is 8h.Reaction result is as follows: conversion of cyclohexane is 9.08%, and the selectivity of cyclohexanone is 45.73%, and the selectivity of cyclohexanol is 28.15%, and the selectivity of acetic acid hexamethylene alcohol ester is 26.12%, does not have carbon dioxide and dirty oil to produce.
Embodiment 9: be initiation material with silica gel, adopt condition and the program identical with embodiment 4, make the Co-Cu-Silica catalyst, wherein, Co and the Cu content in catalyst is respectively 3.6% and 2.0%.Reaction condition is according to embodiment 1, and the reaction time is 8h.Reaction result is as follows: conversion of cyclohexane is 3.6%, and the selectivity of cyclohexanone is 45.10%, and the conversion ratio of cyclohexanol is 54.9%, does not have the generation of acetic acid hexamethylene alcohol ester, does not have carbon dioxide and dirty oil to produce.
Embodiment 10: with silica alumina ratio is that 60 Y zeolite is a starting material, adopts condition and the program identical with embodiment 4, makes catalyst, and wherein, Co and the Cu content in catalyst is respectively 5.2% and 2.5%.Reaction condition is according to embodiment 1, and the reaction time is 8h.Reaction result is as follows: conversion of cyclohexane is 6.14%, and the selectivity of cyclohexanone is 51.52%, and the selectivity of cyclohexanol is 23.95%, and the selectivity of acetic acid hexamethylene alcohol ester is 24.53%, does not have carbon dioxide and dirty oil to produce.
Embodiment 11: the mixed solution that ZSM-5 (silica alumina ratio the is 75) powder that takes by weighing 10g joins the cobalt nitrate of 200ml and ferric nitrate (wherein, the concentration of cobalt nitrate and ferric nitrate is respectively 0.15mol/L and 0.1mol/L) in, carried out ion-exchange in 2 hours 90 ℃ stirred in water bath, left standstill then 5 hours, centrifugation, solid sample is 90 ℃ of oven dry down, and then being put in the high temperature stove 400 ℃ of roastings 3 hours, the content that makes Co and Fe is respectively 4.8% and 3.1% Co-Fe/ZSM-5.Reaction condition is identical with embodiment 1.Reaction result is as follows: cyclohexane conversion is 8.35%, and the selectivity of cyclohexanone is 59.19%, and the selectivity of cyclohexanol is 14.50%, and remaining is an acetic acid hexamethylene alcohol ester, does not have carbon dioxide and dirty oil to produce.
Claims (3)
1. one kind is used for the heterogeneous catalyst that the cyclohexane catalytic oxidation is produced cyclohexanone and cyclohexanol, form by carrier and active metal component, it is characterized in that, described carrier is that silica alumina ratio is 75 modenite, by ion-exchange or dipping approach be incorporated on the described carrier the weight ratio content of reactive metal in catalyst be: Co4.8%, Cu 2.2% make the Co-Cu-mordenite catalyst.
2. one kind is used for the heterogeneous catalyst that the cyclohexane catalytic oxidation is produced cyclohexanone and cyclohexanol, form by carrier and active metal component, it is characterized in that, described carrier is a silica gel, by ion-exchange or dipping approach be incorporated on the described carrier the weight ratio content of reactive metal in catalyst be: Co 3.6%, Cu 2.0% make the Co-Cu-silica-gel catalyst.
3. one kind is used for the heterogeneous catalyst that the cyclohexane catalytic oxidation is produced cyclohexanone and cyclohexanol, form by carrier and active metal component, it is characterized in that, described carrier is that silica alumina ratio is 60 Y zeolite, by the dipping approach be incorporated on the described carrier the weight ratio content of reactive metal in catalyst be: Co 5.2%, Cu 2.5%.
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| 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 |
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| CN102343281A (en) * | 2011-08-05 | 2012-02-08 | 红河学院 | Catalyst for catalyzing and oxidizing cyclohexane into cyclohexanone under liquid phase condition |
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| CN113651685B (en) * | 2021-09-25 | 2024-02-09 | 侯凤芹 | Process for preparing dicarboxylic acids by two-stage oxidation of cyclic alkanes |
| CN114471606B (en) * | 2022-03-01 | 2024-02-13 | 南京先进生物材料与过程装备研究院有限公司 | Titanium dioxide modified manganese cobalt spinel catalyst and preparation method and application thereof |
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