CN105523910A - Oxidation method for cyclohexane - Google Patents
Oxidation method for cyclohexane Download PDFInfo
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Abstract
The invention provides an oxidation method for cyclohexane. The method comprises the step of subjecting a liquid mixture containing cyclohexane and an oxidant to passing through catalyst beds under the condition of oxidation reaction, wherein the catalyst beds comprise a first catalyst bed and a second catalyst bed; on the basis of the flow direction of the liquid mixture, the first catalyst bed is located at the upper stream of the second catalyst bed; a titanium-silicon molecular sieve filled in the first catalyst bed is a hollow titanium-silicon molecular sieve; and the titanium-silicon molecular sieve filled in the second catalyst bed is the titanium-silicon molecular sieve different from the hollow titanium-silicon molecular sieve. The method provided by the invention can effectively prolong the single-way service life of the titanium-silicon molecular sieve used as a catalyst, reduce regeneration frequency of the catalyst, improve production efficiency, and enhance operation stability and prolong the total service life of the catalyst at the same time.
Description
Technical field
The present invention relates to a kind of cyclohexane oxidation processes.
Background technology
Pimelinketone is a kind of important industrial chemicals, is widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Hexalin is also a kind of important industrial chemicals, for hexanodioic acid processed, softening agent and washing composition etc., also for solvent and emulsifying agent.Developing rapidly particularly due to polymeric amide industry, the demand as the pimelinketone (alcohol) preparing nylon-6 and nylon-66 intermediate is annual all more than 1,000,000 tons in the whole world.Now, cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and partial hydrogenation of benzene method, and cyclohexane oxidation process is the main process of industrial production pimelinketone, accounts for more than 90%.But this production process is also considered to minimum one of efficiency in all chemical industry processes.Cyclohexane oxidation synthesizing cyclohexanone process is one of the key and bottleneck of restriction caprolactam production.
The industrial cyclohexane oxidation production pimelinketone that utilizes generally has three kinds of methods: a kind of is adopt cobalt salt to be the catalyzed oxidation of catalyzer, and this method cyclohexane conversion is higher, but makes the easy fouling of reactor owing to forming hexanodioic acid cobalt, is now substantially eliminated.Two is boric acid class catalytic oxidations, and this method initial cost is high, and energy consumption is high, and technique is very complicated, and operation easier is large, and is easy to cause e-quipment and pipe Severe blockage.Three is the non-catalyst oxidations with air direct oxidation, this method effectively prevent the problem of reactor fouling, industrially widely applies, but this complex process, intermediate steps is many, cyclohexane conversion is low, and hexanaphthene internal circulating load is large, and energy consumption is high, pollute also larger, particularly in decomposing cyclohexyl hydrogen peroxide process, pimelinketone (alcohol) selectivity is poor, and yield is low.In addition, a large amount of waste lyes that this process produces, difficult treatment, is still global the difficult problem of environmental protection so far.Therefore, it is possible to for the deficiency of existing technique, work out a kind of cyclohexane conversion high, pimelinketone and hexalin selectivity good, pollute little, the simple novel process of environmentally friendly and technique is of great practical significance.
A kind of new catalytic oxidation material-HTS (TS-1) is disclosed in USP4410501, it has good selective oxidation to hydrocarbon, alcohol, phenol etc., and as being applied to oxidation of phenol preparing benzenediol, cyclohexanone oxamidinating, epoxidation of propylene etc., oneself achieves industrialization.Document (as JCatal, 1995,157:631 ~ 635, AppliedCatalA:Gen2001,211:1 ~ 17 and JNaturalGasChem2001,10:295 ~ 307) is studied titanium molecular sieve catalysis cyclohexane oxidation.Generally speaking, reaction conditions is gentle, and technological process is simple, environmental friendliness.But still the problem such as ubiquity cyclohexane conversion is low, effective utilization ratio of hydrogen peroxide is low, catalyzer is not easily separated simultaneously, and product and catalyst separating cost are improved.
When adopting HTS as catalyst oxidation hexanaphthene, ubiquitous problem is, with the prolongation in reaction times, the catalytic activity of HTS can be on a declining curve, causes oxygenant transformation efficiency, oxygenant effective rate of utilization and desirable oxidation selectivity of product to reduce.
And device operates after for some time, the activity and selectivity of catalyzer can reduce, and namely catalyzer there will be deactivation phenomenom in operation process.At present main settling mode decaying catalyst is carried out in-situ regeneration or ex-situ regeneration to make renewing catalyst activity.Wherein, in-situ regeneration, mainly for the lighter situation of catalyst inactivation, is generally and adopts solvent and/or oxygenant to carry out dipping or the flushing of for some time to decaying catalyst at a certain temperature; Ex-situ regeneration, mainly for the more serious situation of catalyst inactivation, is generally carry out roasting to decaying catalyst.Industrial, general employing first makes renewing catalyst activity through in-situ regeneration, when in-situ regeneration cannot make catalyst activity recover, then adopts ex-situ regeneration.
But when the catalyzer of regeneration puts into operation again, when particularly again putting into operation after in-situ regeneration, the activity and selectivity fluctuation of catalyzer is comparatively large, needs could stablize for a long time; Meanwhile, also need to combine and improve the smooth running that the operation such as temperature of reaction carrys out realization response, but like this can further accelerator activator inactivation reduce desirable oxidation selectivity of product, affect subsequent product refining spearation, be also unfavorable for keeping the safety in production.
Therefore, reduce by product selectivity, the work-ing life of extending catalyst, particularly one way work-ing life, thus the regeneration frequency reaction system remained using HTS as catalyst oxidation hexanaphthene reducing catalyzer needs the technical problem of solution badly.
Summary of the invention
The present invention is intended to solve the cyclohexane oxidation above shortcomings using HTS as catalyzer, a kind of cyclohexane oxidation processes is provided, even if the method can ensure that oxygenant transformation efficiency and desirable oxidation selectivity of product also can be stabilized in higher level by continuous run in long period, and can extend the one way work-ing life of the HTS as catalyzer.
For realizing aforementioned object, the invention provides a kind of cyclohexane oxidation processes, the method comprises: under oxidation reaction condition, makes the liquid mixture containing hexanaphthene and oxygenant flow through beds; Described beds comprises the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, the HTS of described first beds filling is hollow HTS, described hollow HTS is the HTS of MFI structure, the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm;
The HTS of described second beds filling is the HTS being different from hollow HTS.
In the present invention, by by described catalyst bed designs for comprising the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, the HTS of described first beds filling is hollow HTS, described hollow HTS is the HTS of MFI structure, the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm; The HTS of described second beds filling is the HTS being different from hollow HTS.Make it possible to the one way work-ing life of the HTS effectively extended as catalyzer, reduce the regeneration frequency of catalyzer, while enhancing productivity, can operation stability be improved, the terminal life of extending catalyst.
Adopt method oxidizing ethyle alkyl of the present invention, in long-time continuous operational process, comparatively stable oxygenant transformation efficiency can be obtained, higher desirable oxidation selectivity of product.Especially, adopt method of the present invention, the selectivity of pimelinketone is high, thus reduces the difficulty of later separation purifying.
Of the present invention method is simple, is suitable for large-scale application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of cyclohexane oxidation processes, the method comprises: under oxidation reaction condition, makes the liquid mixture containing hexanaphthene and oxygenant flow through beds; Described beds comprises the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, the HTS of described first beds filling is hollow HTS, described hollow HTS is the HTS of MFI structure, the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm;
The HTS of described second beds filling is the HTS being different from hollow HTS.
According to method of the present invention, described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
According to method of the present invention, the HTS that described HTS comprises the first bed and the second bed can be the former powder of HTS, also can be shaping HTS, be preferably shaping HTS.Shaping HTS is generally containing the HTS as activeconstituents and the carrier as binding agent, and wherein, the content of HTS can be conventional selection.Usually, with the total amount of described shaping HTS for benchmark, the content of HTS can be 5-95 % by weight, is preferably 10-95 % by weight, is more preferably 70-95 % by weight; The content of described carrier can be 5-95 % by weight, is preferably 5-90 % by weight, is more preferably 5-30 % by weight.The carrier of described shaping HTS can be conventional selection, as aluminum oxide and/or silicon oxide.The method preparing described shaping HTS is known in the field, no longer describes in detail herein.The granular size of described shaping HTS is also not particularly limited, and can carry out appropriate selection according to concrete shape.As described in shaping HTS be spherical time, the median size of described shaping HTS can be 4-10000 micron, be preferably 5-5000 micron, as 40-2000 micron.Described median size is volume average particle size, and laser particle analyzer can be adopted to measure.
According to method of the present invention, HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.05, is preferably 0.01-0.03, is more preferably 0.015-0.025.
HTS described in second bed can for the common HTS being different from hollow HTS with various topological framework, it comprises all HTS except hollow HTS, such as: described HTS can be selected from 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 (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).HTS described in second bed is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, is more preferably the HTS of MFI structure, is preferably TS-1.
According to method of the present invention, preferably desirable oxidation selectivity of product drop to satisfy condition 1 time, the method also comprises carries out set-up procedure, until desirable oxidation selectivity of product rises to when satisfying condition 2, stops described set-up procedure,
Desirable oxidation selectivity of product S under condition 1, sometime t
twith initial target oxidation products selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S
0ratio S '/S
0be 0.9≤S '/S
0≤ 1;
Described set-up procedure is improve the mass content of oxygenant in described liquid mixture.
According to method of the present invention, more preferably in condition 1, S
t/ S
0<0.9.
According to method of the present invention, more preferably improve the mass content of oxygenant in described liquid mixture with the amplitude in 0.02-5%/sky.
According to method of the present invention, various method can be adopted to improve the mass content of oxygenant in liquid mixture.Such as: the addition of oxygenant during preparation described liquid mixture can be improved to improve the mass content of oxygenant in liquid mixture.When oxygenant provides with the form of oxidizing agent solution, the mass content improving oxygenant in liquid mixture can be realized by the concentration improving oxygenant in oxidizing agent solution, now the consumption of oxidizing agent solution can remain unchanged, also can correspondingly carry out adjusting (such as, the consumption of corresponding reduction oxidizing agent solution, constant rate with between retaining ring hexane and oxygenant), as long as can guarantee that the mass content of oxygenant in liquid mixture is for improving.This mode is specially adapted to use the occasion providing oxygenant (as hydrogen peroxide) with oxidizing agent solution form (as hydrogen peroxide), now can by improving the concentration of oxygenant (as hydrogen peroxide) in oxidizing agent solution (as hydrogen peroxide).In described oxidizing agent solution, the starting point concentration of oxygenant can be conventional selection, can be generally 20-70 % by weight, is preferably 20-50 % by weight.
According to method of the present invention, the weight ratio of the HTS of loading in the HTS of more preferably loading in described first beds and described second beds can be 1-20:1, is preferably 2-10:1, more preferably 2-4:1.
According to method of the present invention, described first beds and the second beds can contain one or more beds separately.When the first beds and/or the second beds contain multiple beds, can for being connected in series between multiple beds, also can for being connected in parallel, can also be series connection and combination in parallel, such as: multiple beds is divided into many groups, beds often in group for being connected in series and/or being connected in parallel, for being connected in series and/or being connected in parallel between each group.Described first beds and described second beds can be arranged on the different zones of same reactor, also can be arranged in different reactors.
According to method of the present invention, it can, for identical, also can be different that liquid mixture flows through the first beds with the superfacial velocity of the second beds.Preferably, liquid mixture flows through the superfacial velocity of the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, wherein, v
1< v
2, the one way work-ing life of HTS can be extended so further.More preferably, v
2/ v
1=1.5-10.Further preferably, v
2/ v
1=2-5.
In the present invention, described superfacial velocity to refer in the unit time by the area of the mass rate (in kg/s) of the liquid mixture of beds whole process and a certain cross section of beds (with m
2meter) ratio.Usually, the quality of the liquid mixture of fixed-bed reactor will can be sent in the unit time as " by the mass rate of the liquid mixture of whole beds in the unit time ".In the present invention, particular requirement be there is no for the superfacial velocity of liquid mixture in the first beds, generally can at 0.001-200kg/ (m
2s) in scope.
Various method can be adopted to carry out the superfacial velocity of regulates liquid mixture in the first beds and the second beds.Such as, the superfacial velocity of regulates liquid mixture can be carried out by the cross-sectional area of selecting catalyst bed.Particularly, the cross-sectional area of described first beds can be made to be greater than the cross-sectional area of described second beds, thus to make v
1< v
2, preferably make v
2/ v
1for 1.5-10, more preferably make v
2/ v
1for 2-5.Superfacial velocity according to expection determines that the method for the cross-sectional area of beds is known in those skilled in the art, no longer describes in detail herein.
According to method of the present invention, when the weight ratio of the HTS of loading in the hollow HTS of loading in described first beds and described second beds is 2-10:1, for realizing v
2/ v
1=2-5, the internal diameter of described first beds and the internal diameter of the second beds are than being 2-5:1.
According to method of the present invention, the residence time of liquid mixture in the first beds is T
1, the total residence time in beds is T, preferably, and T
1/ T=0.3-0.95.More preferably, T
1/ T=0.5-0.85, can obtain the HTS one way work-ing life extended further like this, and obtains higher desirable oxidation selectivity of product.
According to method of the present invention, the temperature of described first beds and the temperature of described beds can be identical or different.From further improving desirable oxidation selectivity of product and the angle extending one way work-ing life of HTS further, preferably the temperature of described first beds is the temperature higher than described second beds.More preferably, the temperature of described first beds is than the temperature height 5-50 DEG C of described second beds, preferred 10-20 DEG C.
According to method of the present invention, when beds contains the first beds and the second beds, fresh material can be supplemented as the case may be between the first beds and the second beds, when the first beds and/or the second beds are multiple beds, fresh cyclohexane can be supplemented between the first beds and/or between the second beds in described liquid mixture as the case may be.Such as: between the first beds and the second beds, between the first beds and/or between the second beds, supplement fresh cyclohexane and optional fresh solvent.But, it should be noted that, liquid mixture when determining superfacial velocity refer to flow through the first beds whole beds (, the whole process of the first beds) and the second beds whole beds (namely, the whole process of the second beds) liquid mixture, and not included in the fresh material introduced between the first beds, between the second beds and between the first beds and the second beds.
According to method of the present invention, described beds only can load HTS, also can contain HTS and inactive filler.In beds, load inactive filler to adjust the amount of HTS in beds, thus the speed of reaction is regulated.When described beds contains HTS and inactive filler, in beds, the content of inactive filler can be 5-95 % by weight.Described inactive filler refers to the filler not having or substantially do not have catalytic activity to oxidizing reaction, and its specific examples can include but not limited to: one or more in quartz sand, ceramic ring and potsherd.
The total amount of described HTS (that is, the total amount of the HTS in the first beds and the second beds) can be selected according to the concrete treatment capacity of system.Usually, with the total amount of the HTS in described first beds and described second beds for benchmark, the weight space velocity of described hexanaphthene can be 0.1-20h
-1, be preferably 0.2-10h
-1.
According to method of the present invention, described oxygenant can be that commonly use various can by the material of cyclohexane oxidation.Preferably, described oxygenant is superoxide.Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, organo-peroxide and peracid.Described organo-peroxide refers to that one or two hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
According to method of the present invention, described hydrogen peroxide is normally that the form of the aqueous hydrogen peroxide solution of 5-70% adds in reaction system with mass percentage concentration, and the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30%, 55% and 70% etc.
The consumption of described oxygenant can be selected according to the amount of hexanaphthene.Usually, the mol ratio of described hexanaphthene and described oxygenant can be 0.1-10:1, is preferably 0.2-5:1, is more preferably 0.2-2:1.
According to method of the present invention, described liquid mixture can contain solvent, also can not contain solvent, preferably also containing at least one solvent, can control speed and the severe degree of reaction so better.The present invention is not particularly limited for the kind of described solvent, and described solvent can either dissolve hexanaphthene and oxygenant or mixing both promoting for various, again can the liquid substance of solubilized target oxidation products.Usually, described solvent can be selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.More preferably, described solvent is acetone and/or butanone.
The present invention is not particularly limited for the consumption of described solvent, can select according to the amount of hexanaphthene and oxygenant.Usually, the weight ratio of described solvent and described hexanaphthene can be 0.1-100:1, is preferably 0.2-80:1.
According to method of the present invention, described oxidation reaction condition can be selected according to the set goal oxidation products.Particularly, the condition that described liquid mixture flows through described first beds and described second beds comprises separately: temperature can be 0-120 DEG C, is preferably 40-100 DEG C; In gauge pressure, pressure can be 0.01-3MPa.
According to method of the present invention, preferably also comprise and send at least one alkaline matter in described liquid mixture, the addition of described alkaline matter makes this liquid mixture pH value be in the scope of 6-9, can obtain better reaction effect like this.More preferably, the addition of described alkaline matter makes the pH value of described liquid mixture be in the scope of 6.5-8.5, is preferably 6.8-8.2., if use alkali, improve the pH value of this liquid mixture further, still can obtain above-mentioned effect time (or being more than 7) in the pH value of the liquid mixture contacted with HTS more than 6.5.The pH value of described liquid mixture refers at 25 DEG C and 1 standard atmosphere pressure, the pH value of this liquid mixture of mensuration.
Herein, described alkaline matter refer to the pH value of its aqueous solution be greater than 7 material.The specific examples of described alkaline matter can include but not limited to: ammonia (that is, NH
3), amine, quaternary ammonium hydroxide and M
1(OH)
n(wherein, M
1for basic metal or alkaline-earth metal, n is and M
1the identical integer of valency).
As described alkaline matter, ammonia can be introduced with the form of liquefied ammonia, also can introduce in form of an aqueous solutions, can also introduce with the form of gas.Concentration as the ammonia (that is, ammoniacal liquor) of aqueous solution form is not particularly limited, and can be conventional selection, such as 1-36 % by weight.
As described alkaline matter, amine refers to hydrogen partial on ammonia or is all replaced the material formed by alkyl, comprises primary amine, secondary amine and tertiary amine.Described amine is specifically as follows the material shown in formula I and/or C
3-C
11heterocyclic amine,
In formula I, R
1, R
2and R
3can be H or C separately
1-C
6alkyl (as C
1-C
6alkyl), and R
1, R
2and R
3be asynchronously H.Herein, C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl and n-hexyl.
The specific examples of amine can include but not limited to: methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tri N-Propyl Amine, di-n-propylamine, Tri-n-Propylamine, Isopropylamine, Diisopropylamine, n-butylamine, di-n-butyl amine, tri-n-butyl amine, sec-butylamine, diisobutyl amine, triisobutyl amine, tert-butylamine, n-amylamine, two n-amylamines, tri-n-amyl amine, neopentyl amine, isobutylcarbylamine, di-iso-amylamine, tri-isoamylamine, tertiary amylamine, normal hexyl Amine and n-octyl amine.
Described heterocyclic amine is compound finger ring having nitrogen-atoms and this nitrogen-atoms has lone-pair electron.Described heterocyclic amine can be such as one or more in substituted or unsubstituted pyrroles, substituted or unsubstituted Pyrrolidine, substituted or unsubstituted pyridine, substituted or unsubstituted hexahydropyridine, substituted or unsubstituted imidazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted quinoline, substituted or unsubstituted dihydroquinoline, substituted or unsubstituted tetrahydroquinoline, substituted or unsubstituted decahydroquinoline, substituted or unsubstituted isoquinoline 99.9 and substituted or unsubstituted pyrimidine.
As described alkaline matter, quaternary ammonium hydroxide is specifically as follows the material shown in formula II,
In formula II, R
4, R
5, R
6and R
7can be C separately
1-C
6alkyl (as C
1-C
6alkyl).Described C
1-C
6alkyl comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, its specific examples can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.
The specific examples of described quaternary ammonium hydroxide can include but not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprising four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl-ammonium hydroxide and tetra-tert ammonium hydroxide) and four pentyl ammonium hydroxide.
As described alkaline matter, M
1(OH)
nfor the oxyhydroxide of alkali-metal oxyhydroxide or alkaline-earth metal, such as, can be sodium hydroxide, potassium hydroxide, magnesium hydroxide, hydrated barta and calcium hydroxide.
According to method of the present invention, described alkaline matter can directly use, and uses after also described alkaline matter can being mixed with solution.Can send in fixed-bed reactor after solvent by alkaline matter and oxygenant and optionally, described mixing can be carried out outside reactor, also can carry out in reactor, be not particularly limited.
According to method of the present invention, consider from the angle of the technique effect implemented, preferred described alkaline matter is pyridine.
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used according to Zeolites, the method preparation described in 1992, Vol.12:943-950, its titanium oxide content is 2.5 % by weight;
Hollow HTS used is be the hollow HTS of HTS purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd, and its titanium oxide content is 2.5 % by weight.
Ti-MCM-41 HTS used is that prepared by the method described in 1994,147-148, with oxide basis, the titanium content of this HTS is 3.0 % by weight according to Corma etc. at Chem.Commun..
Ti-Beta HTS used is that prepared by the method described in 1997,677-678, with oxide basis, the titanium content of this HTS is 2.6 % by weight according to TakashiTatsumi etc. at J.Chem.Soc.Chem.Commun..
In following examples and comparative example, adopt vapor-phase chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate oxygenant transformation efficiency, pimelinketone selectivity on this basis respectively:
Cyclohexane conversion (%)=(participating in the mole number of the hexanaphthene of the mole number/add of the hexanaphthene of reaction) × 100;
Pimelinketone selectivity (%)=(mole number of the hexanaphthene of mole number/reaction consumption of the pimelinketone that reaction generates) × 100.
In the present invention, in embodiment and comparative example, the preparation method of microspherical catalyst used is as follows: under normal pressure and 60 DEG C of conditions, is first joined in the TPAOH aqueous solution by silicoorganic compound tetraethoxy and mixes, and stirs hydrolysis 5h and obtains colloidal solution; Then HTS or hollow HTS are added to mix among above-mentioned gained colloidal solution and obtain slurries, and wherein the mass ratio of HTS or hollow HTS, silanes, TPAOH and water is 100:25:5:250; After above-mentioned slurries are continued to stir 2h, after conventional mist projection granulating, roasting can obtain the catalyzer of the present invention's microballoon shape used.
Embodiment 1-14 is for illustration of method of the present invention.
Embodiment 1
Reaction is carried out in two micro fixed-bed reactors be connected in series, wherein, loading a cross section in each reactor is circular isometrical beds, with the flow direction of liquid material for benchmark, the internal diameter being arranged in the first beds of first reactor of upstream is 2:1 with the ratio of the internal diameter of the second beds of second reactor being arranged in downstream, (volume average particle size is the spherical catalyst of 500 μm, and the density of catalyzer is 0.70g/cm to load shaping hollow HTS in first beds
3), (volume average particle size is the spherical catalyst of 500 μm, and density is 0.76g/cm to load shaping titanium-silicon molecular sieve TS-1 in the second beds
3), the weight ratio of hollow HTS and titanium-silicon molecular sieve TS-1 is 2:1.
Using hexanaphthene, as oxygenant hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) and send into as the acetone of solvent from the bottom of first reactor, by the first beds to contact with the shaping hollow HTS filled in wherein; The liquid mixture exported from first reactor then enters second reactor, by the second beds to contact with the shaping titanium-silicon molecular sieve TS-1 filled in wherein continuously.
Wherein, the mol ratio of hexanaphthene and hydrogen peroxide is 1:2, and the pH value in first reactor and second reactor is 6.8, and pH value regulator is ammoniacal liquor (concentration is 25 % by weight), and the weight ratio of solvent and hexanaphthene is 15:1; Temperature in first beds and the second beds is controlled as 80 DEG C, 70 DEG C, and the pressure in first reactor and second reactor is respectively 0.5MPa; With the total amount of the HTS in the first beds and the second beds for benchmark, the weight space velocity of hexanaphthene is 5h
-1.
The composition of the reaction mixture exported from reactor is monitored continuously, at pimelinketone selectivity S in reaction process
twith initial (reaction proceeds to 0.5 little sampling and measuring constantly) pimelinketone selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0during <0.9 (, satisfy condition 1 time), the mass content (improve by means of only the concentration of hydrogen peroxide improved in hydrogen peroxide, the consumption of hydrogen peroxide remains unchanged) of hydrogen peroxide in liquid mixture is improved until pimelinketone selectivity S ' and initial pimelinketone selectivity S with the amplitude in 0.02-5%/sky
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving oxygenant mass content.
Run continuously under these conditions, in operational process, detect the composition of the reaction mixture exported from second reactor, and calculate cyclohexane conversion, pimelinketone selectivity, wherein, the reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Comparative example 1
Adopt the method oxidizing ethyle alkyl identical with embodiment 1, unlike, the shaping hollow HTS of the shaping titanium-silicon molecular sieve TS-1 equivalent in the second beds replaces.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Comparative example 2
Adopt the method oxidizing ethyle alkyl identical with embodiment 1, unlike, the shaping titanium-silicon molecular sieve TS-1 of the shaping hollow HTS equivalent in the first beds replaces.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Comparative example 3
Adopt the method oxidizing ethyle alkyl identical with embodiment 1, unlike, the shaping titanium-silicon molecular sieve TS-1 of the shaping hollow HTS equivalent in the first beds replaces, and the shaping hollow HTS of the shaping titanium-silicon molecular sieve TS-1 equivalent in the second beds replaces.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Embodiment 2
Adopt the method oxidizing ethyle alkyl identical with embodiment 1, unlike, (volume average particle size is the spherical catalyst of 500 μm to the shaping HTS Ti-MCM-41 of the shaping titanium-silicon molecular sieve TS-1 equivalent in the second beds, and density is 0.61g/cm
3) replace.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Embodiment 3
Adopt the method oxidizing ethyle alkyl identical with embodiment 1, unlike, (volume average particle size is the spherical catalyst of 500 μm to the shaping HTS Ti-Beta of the shaping titanium-silicon molecular sieve TS-1 equivalent in the second beds in second reactor, and density is 0.77g/cm
3) replace.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in Table 1.
Table 1
The data of embodiment 1 with comparative example 1-3 are compared and can find out, hollow HTS and HTS are being combinationally used, and when making hollow HTS be positioned at HTS upstream, the one way work-ing life of apparent speed apparent speed that liquid mixture flows through hollow HTS being less than flow through titanium-silicon molecular sieve TS-1 extending catalyst further.
Embodiment 4
Reaction is carried out in two micro fixed-bed reactors be connected in series, wherein, loading a cross section in each reactor is circular isometrical beds, with the flow direction of liquid material for benchmark, the internal diameter being arranged in the first beds of first reactor of upstream is 4.4:1 with the ratio of the internal diameter of the second beds of second reactor being arranged in downstream, shaping hollow HTS (identical with embodiment 1) is loaded in first beds, shaping titanium-silicon molecular sieve TS-1 (identical with embodiment 1) is loaded in second beds, the weight ratio of hollow HTS and titanium-silicon molecular sieve TS-1 is 4:1.
Using hexanaphthene, as oxygenant hydrogen peroxide (providing using the form of the hydrogen peroxide of 30 % by weight) and send into as the acetone of solvent from the bottom of first reactor, by the first beds to contact with the shaping hollow HTS filled in wherein (identical with embodiment 1); The liquid mixture exported from first reactor then enters the second reactor, continuously by the second beds to contact with the shaping titanium-silicon molecular sieve TS-1 filled in wherein (identical with embodiment 1).
Wherein, the mol ratio of hexanaphthene and hydrogen peroxide is 1:4, and the pH value in first reactor and second reactor is 7.2, and pH value regulator is pyridine solution (concentration is 25 % by weight), and the weight ratio of solvent and hexanaphthene is 5:1; Temperature in first beds and the second beds is controlled as 60 DEG C, 40 DEG C, and the pressure in first reactor and second reactor is respectively 0.3MPa; With the total amount of the HTS in the first beds and the second beds for benchmark, the weight space velocity of hexanaphthene is 6h
-1.
The composition of the reaction mixture exported from reactor is monitored continuously, at pimelinketone selectivity S in reaction process
twith initial (reaction proceeds to 0.5 little sampling and measuring constantly) pimelinketone selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0during <0.9 (, satisfy condition 1 time), the mass content (improve by means of only the concentration of hydrogen peroxide improved in hydrogen peroxide, the consumption of hydrogen peroxide remains unchanged) of hydrogen peroxide in liquid mixture is improved until pimelinketone selectivity S ' and initial pimelinketone selectivity S with the amplitude in 0.02-5%/sky
0ratio S '/S
0be 0.9≤S '/S
0when≤1 (that is, satisfy condition 2 time), stop improving oxygenant mass content.
Run continuously under these conditions, in operational process, detect the composition of the reaction mixture exported from second reactor, and calculate cyclohexane conversion, pimelinketone selectivity, wherein, the reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in table 2.
Embodiment 5
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, unlike, under the condition that in first beds and the second beds, the loadings of catalyzer is constant, adjust the internal diameter of the first beds and the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 3.5:1.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in table 2.
Embodiment 6
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, unlike, under the condition that in first beds and the second beds, the loadings of catalyzer is constant, adjust the internal diameter of the first beds and the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 2:1.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in table 2.
Embodiment 7
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, unlike, under the condition that in first beds and the second beds, the loadings of catalyzer is constant, adjust the internal diameter of the first beds and the second beds, make the ratio of the internal diameter of the first beds and the internal diameter of the second beds be 1:2.
Reaction times is that 2 hours, 360 hours and 720 little results are constantly listed in table 2.
Embodiment 8
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, unlike, pH value is 6.
Embodiment 9
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, unlike, pH value regulator is ammoniacal liquor (concentration is 25 % by weight).
Embodiment 10
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, be controlled as 60 DEG C, 60 DEG C unlike the temperature in, the first beds and the second beds.
Embodiment 11
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, be controlled as 40 DEG C, 60 DEG C unlike the temperature in, the first beds and the second beds.
Embodiment 12
Adopt the method identical with embodiment 4, unlike, do not carry out described set-up procedure.
Embodiment 13
Adopt the method identical with embodiment 1, unlike, pH value regulator is pyridine solution (concentration is 25 % by weight).
Embodiment 14
Adopt the method oxidizing ethyle alkyl identical with embodiment 4, be controlled as 60 DEG C, 25 DEG C unlike the temperature in, the first beds and the second beds.
Table 2
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (14)
1. a cyclohexane oxidation processes, the method comprises: under oxidation reaction condition, makes the liquid mixture containing hexanaphthene and oxygenant flow through beds; Described beds comprises the first beds and the second beds, with the flow direction of liquid mixture for benchmark, described first beds is positioned at the upstream of described second beds, the HTS of described first beds filling is hollow HTS, described hollow HTS is the HTS of MFI structure, the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm;
The HTS of described second beds filling is the HTS being different from hollow HTS.
2. method according to claim 1, wherein, the HTS of described second beds filling is TS-1.
3. method according to claim 1 and 2, wherein, desirable oxidation selectivity of product drop to satisfy condition 1 time, the method also comprises carries out set-up procedure, until desirable oxidation selectivity of product rises to when satisfying condition 2, stops described set-up procedure,
Desirable oxidation selectivity of product S under condition 1, sometime t
twith initial target oxidation products selectivity S
0ratio S
t/ S
0be 0.85≤S
t/ S
0<1;
Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation products selectivity S
0ratio S '/S
0be 0.9≤S '/S
0≤ 1;
Described set-up procedure is improve the mass content of oxygenant in described liquid mixture.
4. method according to claim 3, wherein, in condition 1, S
t/ S
0<0.9.
5. method according to claim 3, wherein, improves the mass content of oxygenant in described liquid mixture with the amplitude in 0.02-5%/sky.
6. method according to claim 1 and 2, wherein, the weight ratio of the HTS that the hollow HTS of described first beds filling and described second beds load is 1-20:1, is preferably 2-10:1.
7. method according to claim 1 and 2, wherein, the superfacial velocity that described liquid mixture flows through the first beds is v
1, the superfacial velocity flowing through the second beds is v
2, v
1< v
2; Preferably, v
2/ v
1=1.5-10.
8. method according to claim 1 and 2, wherein, the residence time of described liquid mixture in the first beds is T
1, the total residence time in beds is T, preferably, and T
1/ T=0.5-0.85.
9. method according to claim 1 and 2, wherein, the temperature of described first beds is higher than the temperature of described second beds; Preferably, the temperature of described first beds is than the temperature height 5-50 DEG C of described second beds.
10. method according to claim 1 and 2, wherein, described liquid mixture is also containing at least one solvent, and the weight ratio of described solvent and described hexanaphthene is 0.1-100:1, and described solvent is acetone and/or butanone.
11. methods according to claim 1 and 2, wherein, described oxygenant is superoxide.
12. methods according to claim 1 and 2, wherein, the mol ratio of hexanaphthene and described oxygenant is 0.1-10:1.
13. methods according to claim 1, wherein, the method also comprises sends at least one alkaline matter in described liquid mixture, and the feeding amount of described alkaline matter makes the pH value of described liquid mixture be in the scope of 6-9.
14. methods according to claim 1, wherein, the condition that described liquid mixture flows through described first beds and described second beds comprises separately: temperature is 0-120 DEG C; In gauge pressure, pressure is 0.01-3MPa; With the total amount of the HTS in described first beds and described second beds for benchmark, the weight space velocity of described hexanaphthene is 0.1-20h
-1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654684A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院大连化学物理研究所 | It a kind of organic silicon sphere catalyst of B/L acid modification and prepares and its application |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
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2014
- 2014-09-29 CN CN201410515123.9A patent/CN105523910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4410501A (en) * | 1979-12-21 | 1983-10-18 | Snamprogetti S.P.A. | Preparation of porous crystalline synthetic material comprised of silicon and titanium oxides |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
| CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108654684A (en) * | 2017-03-29 | 2018-10-16 | 中国科学院大连化学物理研究所 | It a kind of organic silicon sphere catalyst of B/L acid modification and prepares and its application |
| CN108654684B (en) * | 2017-03-29 | 2020-09-04 | 中国科学院大连化学物理研究所 | B/L acid modified organic silicon ball catalyst, preparation and application thereof |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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