Embodiment
Below in conjunction with accompanying drawing further explain method provided by the invention.
The invention provides a kind of method of cyclohexane oxidation; This method is carried out in a kind of film pipe reactor (as shown in Figure 1); Said film pipe reactor comprises tubular reactor 1 and membrane structure 2; The exit end of said tubular reactor 1 and said membrane structure 2 are tightly connected, said membrane structure 2 be set to allow in the said tubular reactor 1 liquid material through and do not allow solid materials to pass through, this method is included under the oxidation reaction condition; The liquid feeding that will contain hexanaphthene, aqueous hydrogen peroxide solution and organic solvent is sent into the tubular reactor 1 from the opening for feed of film pipe reactor; Contact with the HTS in the tubular reactor 1, the product after the contact carries out solid-liquid separation through the membrane structure 2 that the exit end with said tubular reactor 1 is tightly connected, and obtains liquid material.
Method of the present invention can successive reaction also can rhythmic reaction, and normally under the condition of successive reaction, carry out in the industrial application process, therefore, under the preferable case, method of the present invention adopts successive reaction.
According to the method for the invention; Can realize the object of the invention as long as the exit end of said film pipe reactor and said membrane structure 2 are tightly connected, but under the preferable case, said equipment comprises two said membrane structures 2; The two ends of tubular reactor 1 are tightly connected with a said membrane structure 2 respectively; This tubular reactor 1 can be horizontal reactor thus, also can be vertical reactor, and when being vertical reactor; Can adopt stream mode or downward stream mode charging on the reaction mass, stream mode charging on the preferred feed.
According to the present invention; The present invention does not have particular requirement to the various parameters of said membrane structure; Be tightly connected as long as guarantee the exit end and the said membrane structure 2 of said tubular reactor 1, said membrane structure 2 be set to allow in the said tubular reactor 1 liquid material through and do not allow solid materials to pass through to get final product.Generally speaking; Membrane structure with above-mentioned functions can be filtering membrane or film pipe; Said filtering membrane or film pipe all can be made according to prior art, if the parameter requirement according to the invention of the membrane structure that is provided with, and said important parameter aperture with membrane structure of above-mentioned functions also can be selected according to the concrete catalyst Ti-si molecular sieves particulate size that adopts; The aperture of generally speaking said membrane structure 2 is 5-500nm, is preferably 10-100nm.When said membrane structure was the film pipe, this film pipe can also can make an end of film pipe and tubular reactor 1 be tightly connected for the inside of the exit end that is positioned at tubular reactor 1 fully, and the other end stretches out the outside of tubular reactor 1.
The present invention does not have particular requirement to the said method that is tightly connected, and can carry out with reference to prior art, repeats no more at this.
According to equipment of the present invention; In order to make equipment of the present invention be applicable to industrial applications more; Said tubular reactor 1 is divided at least two sections; Separate through barrier film 3 between adjacent two sections, this barrier film 3 be set to allow in the said tubular reactor 1 liquid material through and do not allow solid materials to pass through.
According to the present invention, the present invention does not have particular requirement to the material of said barrier film 3, as long as can satisfy aforementioned requirement of the present invention; And contriver of the present invention thinks; Based on foregoing description of the present invention, the needs that those skilled in the art can practical situation are selected barrier film, as being set to have identical aperture by barrier film; Also can need according to concrete production, barrier film is set to different apertures.
According to the present invention, under the preferable case, said tubular reactor 1 can be divided into the 2-50 section, and every section length can be set to 0.2-5m.Can be direct contact between adjacent two sections, also can install and production operation for ease of equipment that also can exist between adjacent two sections at interval, those skilled in the art all can know this, repeat no more at this according to the plant location needs.
According to the present invention; For guaranteeing that membrane structure 2 and barrier film 3 are not stopped up by titanium-silicon molecular sieve catalyst; Under the preferable case; Said film pipe reactor also comprises the recoiling device (not shown), and said recoiling device is used to provide gas stream or the liquid stream that said membrane structure 2 and barrier film 3 are carried out back flushing.The present invention does not have particular requirement to said recoiling device, as long as thereby can realize being used to providing gas stream or liquid stream that said membrane structure 2 and barrier film 3 are carried out back flushing to realize said membrane structure 2 is carried out back flushing with barrier film 3.
According to the present invention; The flow of said gas stream or liquid stream can be selected according to factors such as liquid hourly space velocity, catalyst particle size and catalyst concns; And the flow of gas stream or liquid stream can carry out manually or automatically regulating according to practical situation; Those skilled in the art all can know this, repeat no more at this.
According to the present invention, said gas stream can be various gases of not participating in oxidizing reaction, for example can be rare gas element, and said liquid stream is preferably hexanaphthene, said organic solvent or said liquid material.
According to the method for the invention, in order to be applicable to the serialization operation of a whole set of cyclohexane oxidation technology more, said film pipe reactor can also comprise and be used for reaction mass and reaction product are carried out isolating separating unit 4.This separating unit 4 can be variously can realize the isolating device of liquid liquid; Under the preferable case; This separating unit 4 can comprise opening for feed, product discharge port and reaction mass discharge port, and under the preferable case, the opening for feed of said separating unit is communicated with the discharge port of said tubular reactor; Said reaction mass discharge port is communicated with the opening for feed of said tubular reactor, and is as shown in Figure 1.More have under the selection condition, said separating unit is a rectifying tower.When adopting this film pipe reactor; Method of the present invention can also be with through said separating unit liquid material being carried out rectifying; Reaction mass after obtaining separating and reaction product, and the reaction mass after will separating is sent into the tubular reactor 1 from the opening for feed of film pipe reactor and is recycled.
According to the present invention, the condition of said oxidizing reaction can be the employing HTS/H of routine
2O
2The oxidizing condition of system catalyzed oxidation hexanaphthene, the mass ratio that generally comprises hexanaphthene, hydrogen peroxide, water and organic solvent is 1: 0.003-1: 0.001-5: 0.5-30 is preferably 1: 0.03-0.8: 0.1-3: 3-15; The temperature of contact is 30-150 ℃, is preferably 50-120 ℃; The pressure of contact is 0.01-2MPa, is preferably 0.1-0.5MPa, and liquid hourly space velocity is 0.5-10h
-1, be preferably 0.5-5h
-1The weight ratio of liquid material and HTS is 1: 0.01-0.3 is preferably 1: 0.03-0.12.
Among the present invention; Said liquid hourly space velocity is the definition of the conventional liquid hourly space velocity of using in this area; Be a kind of representation of air speed, its meaning is the per hour volume of treatment solution phase reaction thing of unit reaction volume (for the reaction of adopting solid catalyst, then being per volume of catalyst).
Among the present invention, said pressure refers to the gauge pressure in the reaction system.
According to the present invention, organic solvent can be organic solvent commonly used, as being in alcohol, ketone, acid, nitrile and the halohydrocarbon one or more.Said alcohol can be alcohols materials such as methyl alcohol, ethanol, and said ketone can be organic ketone materials such as acetone, butanone, and said acid can be organic acid substances such as acetate.And contriver of the present invention finds in research process unexpectedly; When adopting nitrile and/or halohydrocarbon as solvent; Not only can increase substantially the yield of conversion of cyclohexane and hexalin; And adopt the reaction system separation of these two kinds of solvents to be more prone to, so the preferred said solvent of the present invention is aforesaid nitrile and/or halohydrocarbon.
Contriver of the present invention finds in research process unexpectedly; When using with said nitrile and halohydrocarbon into organic solvent; Can make that conversion of cyclohexane and hexalin yield obtain further to improve; Be under the special preferable case, said organic solvent is the mixture of nitrile and halohydrocarbon, and the mass ratio that is preferably nitrile and halohydrocarbon is 0.1-10: 1.At organic solvent is under the situation of above-mentioned mixed solvent, and the temperature of said contact is preferably 50-120 ℃, and more preferably 60-110 ℃ the time, the hexalin yield obviously improves.Although when adopting two kinds of solvents, the yield of conversion of cyclohexane, title product has further raising, yet the reaction system of two kinds of solvents; Make troubles for follow-up mask work, therefore, generally speaking; Can select whether need adopt two kinds of solvents to react according to the objectives in the concrete industrial production; As mainly pursue the yield of conversion of cyclohexane and title product aborning, can be chosen under the reaction system of aforementioned two kinds of solvents and react, otherwise; If integrated artistic requires comparatively strict words to sepn process; Then can be chosen under preferred a kind of solvent system and react, those skilled in the art all can know this, give unnecessary details no longer one by one at this.
All can realize the object of the invention although adopt above-mentioned nitrile and/or halogenated hydrocarbon solvent; Under the preferable case; Said nitrile is mononitriles and/or the dinitrile of C1-C10, is preferably mononitriles and/or the dinitrile of C2-C8, and is further preferred; Said nitrile is one or more in acetonitrile, propionitrile, valeronitrile, the adiponitrile, is preferably acetonitrile and/or adiponitrile; Said halohydrocarbon is to replace the naphthenic hydrocarbon of C6-C10 by the alkane of one and/or a plurality of identical or different substituted C1-C10 of halogen atom and/or by one and/or a plurality of identical or different halogen atom, further is preferably dichloro-alkane and/or the three chloro alkane of C1-C6, more preferably methylene dichloride, trichloromethane, 1,1-ethylene dichloride, 1,2-ethylene dichloride, 1; 1,1-trichloroethane, vinyl trichloride, 1; 2-propylene dichloride, 2,2-propylene dichloride, 1,3-propylene dichloride, 1,2; 3-trichloropropane, 1,2-dichlorobutane, 2,3-dichlorobutane, 1,4-dichlorobutane, 1; 2-dichloropentane, 2,2-dichloropentane, 1,3-dichloropentane, 2,3-dichloropentane, 3; 3-dichloropentane, 1,4-dichloropentane, 2,4-dichloropentane, 1,2; 5-three chloropentanes, 1,1,5-three chloropentanes and 1, one or more in the 2-dichloro hexanaphthene.
Contriver of the present invention discovers that when said solvent was nitrile, when the temperature of said contact was preferably 60-120 ℃, conversion of cyclohexane and hexalin yield can further improve; Perhaps when said solvent was halohydrocarbon, when the temperature of said contact was 50-90 ℃, conversion of cyclohexane and hexalin yield can further improve.
According to the present invention; HTS in the said titanium-silicon molecular sieve catalyst can be the HTS of routine; Can for modification also can be for non-modification, be preferably at least a in the HTS (like Ti-β) of HTS (like TS-2), BETA structure of HTS (like TS-1), the MEL structure of MFI structure; More preferably having structural formula is xTiO
2SiO
2, wherein, x is 0.0001-0.04, is preferably 0.01-0.03, more preferably the HTS of 0.015-0.025.
In the present invention; Said HTS can be commercially available; Also can prepare; The method for preparing said HTS has been conventionally known to one of skill in the art, for example, and can be with reference to [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) With HydrogenPeroxide Journal of Natural Gas Chemistry 2001; 10 (4): 295-307] the method preparation described in also can make with reference to the disclosed method for preparing catalyzer among the CN101279959A.
More preferably, the HTS in the said titanium-silicon molecular sieve catalyst is the MFI structure, and HTS crystal grain is hollow structure, and the radical length of the cavity part of this hollow structure is 5-300nm, and said HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is for being no less than 70 milligrams/gram; There is hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this HTS and the desorption isotherm; HTS with said structure and character is commonly referred to as hollow HTS; The commercial HTS that is called, its correlation parameter and preparation method thereof can be referring to CN1301599A.
Following embodiment will further explain the present invention, but therefore not limit the present invention.
Used reagent is commercially available chemically pure reagent among Comparative Examples and the embodiment.
(long manufactured is built in the Hunan to the Industrial products that used hollow HTS HTS is the said HTS of CN1301599A among the embodiment; Through the X-ray diffraction analysis is the HTS of MFI structure; Have hysteresis loop between the adsorption isothermal line of the low temperature conditioning absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15-180nm; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram), titanium oxide content is 2.5 weight %.
Used traditional HTS (TS-1) is by document [CyclohexaneOxidation Catalyzed by Titanium Silicalite (T S-1) With Hydrogen PeroxideJournal of Natural Gas Chemistry 2001 among the embodiment; 10 (4): 295-307] the 296th page of (TS-1) sieve sample that the capable described method of 9-24 is prepared in, the content of titanium oxide is 2.5 weight %.
Among the present invention, adopt gc to carry out each analysis of forming in the system, carry out quantitatively all can carrying out, calculate the evaluation indexes such as yield and selectivity of transformation efficiency, the product of reactant on this basis with reference to prior art through proofreading and correct normalization method.
Among the present invention, the conversion of cyclohexane calculation formula is following:
Component optionally calculation formula is following:
The calculation formula of component yield is following:
V
Hexalin=S
Hexalin* X
Hexanaphthene
Wherein, X is a transformation efficiency; S is a selectivity; Y is a yield; M is the quality of component; N is the amount of substance of component; M wherein
0And n
0Quality and molar weight before expression is reacted respectively.
All adopt film pipe reactor shown in Figure 1 in the embodiment of the invention; Wherein the total height of tubular reactor is 2m; The diameter of tubular reactor is 1.2cm; Membrane structure (with the repacking that the inferior membrane separation technique in sky, Nanjing ltd produces ceramic membrane, the aperture is 100nm) is tightly connected with tubular reactor, and adopts three barrier films (with the repacking of the inferior membrane separation technique in sky, Nanjing ltd production ceramic membrane; The aperture is 100nm); Tubular reactor evenly is divided into 4 sections, and film pipe reactor of the present invention also comprises the separator (separator is a rectifying tower) that is used for separating reaction material and reaction product, the content of the HTS in the film pipe reactor in every section tubular reactor is identical.(temperature of reaction being provided) through on the tubular reactor of film pipe reactor, twining the heating zone.
Embodiment 1
According to hexanaphthene and ydrogen peroxide 50 (concentration is 27.5 weight %) and solvent 1; The mass ratio of 2-propylene dichloride (96.8 ℃ of boiling points) is that 1: 1.72: 15 ratio is from the opening for feed continuously feeding of film pipe reactor; The weight ratio of HTS and liquid material is 0.04: 1, liquid hourly space velocity 1h
-1Temperature in the film pipe reactor is 60 ℃; Pressure is 0.2MPa, then will carry out separating of reaction product and reaction mass from the separating unit that the mixture that discharge port comes out is sent into the film pipe reactor, reaction mass is continued to be fed in the tubular reactor react; Sampling analysis behind the system stable operation 4h records conversion of cyclohexane, keto-alcohol selectivity and hexalin yield and sees table 1.
Embodiment 2
Identical with the method for embodiment 1, different is that solvent is 1, the 4-dichloropentane, and 1, the mass ratio of 4-dichloropentane and hexanaphthene is 5: 1, and the temperature in the film pipe reactor is 80 ℃, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 3
Identical with the method for embodiment 1, different is that solvent is an adiponitrile, and the mass ratio of adiponitrile and hexanaphthene is 10: 1, and the temperature in the film pipe reactor is 110 ℃, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 4
Identical with the method for embodiment 3, different is that solvent is an acetonitrile, and the temperature in the film pipe reactor is 70 ℃, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 5
Identical with the method for embodiment 1, different is that solvent is a trichloromethane, and temperature of reaction is 50 ℃.
Embodiment 6
Identical with the method for embodiment 1, different is, solvent is 1,1, the 5-trichloropropane, and temperature of reaction is 90 ℃.
Embodiment 7
Identical with the method for embodiment 1, different is, solvent 1,2-propylene dichloride are by 1, and the mixed solvent of 2-propylene dichloride and propionitrile replaces, and the mass ratio of the two is 1: 1, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 8
Identical with the method for embodiment 3, different is solvent adiponitrile is by 1, and the mixed solvent of 2-propylene dichloride and adiponitrile replaces; Heating medium is a hexanaphthene; And 1, the mass ratio of 2-propylene dichloride and adiponitrile is 1: 9, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 9
Identical with the method for embodiment 4, different is solvent acetonitrile is by acetonitrile and 1, and the 3-propylene dichloride replaces, and acetonitrile and 1, and the mass ratio of 3-propylene dichloride is 1: 9, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 10
Identical with the method for embodiment 1, different is solvent 1, and the 2-propylene dichloride is replaced by n-propyl chloride, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 11
Identical with the method for embodiment 1, different is that solvent is an acetone, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 12
Identical with the method for embodiment 1, different is that solvent is an acetate, and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Embodiment 13
Identical with the method for embodiment 1, different is that catalyzer is the catalyzer that contains conventional HTS (TS-1), and conversion of cyclohexane, keto-alcohol selectivity and hexalin yield are seen table 1.
Table 1
Embodiment |
Cyclohexane conversion/% |
Keto-alcohol selectivity/% |
Hexalin yield/% |
1 |
74% |
100% |
59% |
2 |
73% |
100% |
60% |
3 |
73% |
100% |
61% |
4 |
74% |
100% |
62% |
5 |
73% |
100% |
60% |
6 |
73% |
100% |
61% |
7 |
78% |
100% |
69% |
8 |
77% |
100% |
67% |
9 |
78% |
100% |
66% |
10 |
64% |
100% |
47% |
11 |
47% |
90% |
17% |
12 |
34% |
85% |
17% |
13 |
24% |
90% |
14% |
Can find out by table 2; Adopt method of the present invention; The yield of conversion of cyclohexane and hexalin is all higher, and the present invention has effectively realized the isolating beneficial effect of limit coronite because in the film pipe reactor, react; Overcome rhythmic reaction solid-liquid separation difficulty, successive reaction is sluggish problem under the condition of preformed catalyst.