CN104415743A - Regenerating method of titanium-containing catalyst - Google Patents
Regenerating method of titanium-containing catalyst Download PDFInfo
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- CN104415743A CN104415743A CN201310407445.7A CN201310407445A CN104415743A CN 104415743 A CN104415743 A CN 104415743A CN 201310407445 A CN201310407445 A CN 201310407445A CN 104415743 A CN104415743 A CN 104415743A
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Abstract
The invention provides a regenerating method of a titanium-containing catalyst, wherein the regenerating method comprises the following steps: enabling an inactivated titanium-containing catalyst to be in first contact with an aqueous hydrogen peroxide solution to obtain a first mixture; and enabling the first mixture to be in second contact with an alkaline substance solution. The inactivated titanium-containing catalyst is regenerated according to the regenerating method disclosed by the invention, so that the relative crystallinity and micropore specific surface area of the regenerated titanium-containing catalyst are basically completely recovered, and the activity of the regenerated titanium-containing catalyst is greatly improved in comparison with that of the untreated titanium-containing catalyst.
Description
Technical field
The present invention relates to a kind of renovation process of titanium-containing catalyst.
Background technology
HTS be last century early eighties start develop novel hetero-atom molecular-sieve.The TS-1 having MFI type structure synthesized at present, the TS-2 of MEL type structure, and there is the Ti-MWW etc. compared with macroporous structure.This molecular sieve analog is to many organic oxidizing reactions, the reactions such as the oxidation of the epoxidation of such as alkene, arene hydroxylation, cyclohexanone oximate, alcohol have excellent selective oxidation performance and higher catalytic activity, and they have a good application prospect as redox-type molecular sieve catalyst.
TS-1 molecular sieve is introduced by transition metal titanium to have a kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of ZSM-5 structure.TS-1 molecular sieve not only has the catalysed oxidn of titanium, but also the shape of selecting with ZSM-5 molecular sieve acts on and excellent stability.Because TS-1 molecular sieve is in organic oxidation reaction, free of contamination low concentration hydrogen peroxide can be adopted as oxidant, avoid the problem of oxidizing process complex process and contaminated environment, it has unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and there is good reaction selectivity, therefore there is great prospects for commercial application.But usually can be deteriorated at operation a period of time rear catalyst catalytic performance, there is deactivation phenomenom in catalyst.Cause the reason of catalysqt deactivation may be that impurity owing to introducing in synthesis of molecular sieve process or byproduct of reaction are gathered in plug-hole etc. in catalyst micropore.
EP0100119 discloses a kind of molecular sieve containing titanium epoxidation of propylene that adopts to prepare the method for expoxy propane.In course of reaction, the easy inactivation of HTS, this method proposes two kinds of regenerative processes, and one is employing 550 DEG C of high-temperature roastings, and another kind adopts the solvent wash used in methyl alcohol or course of reaction.Two kinds of regenerative processes respectively have weak point, and first the first renovation process needs through super-dry at high-temperature roasting procatalyst, then need to cool after high-temperature roasting, need lot of energy and take equipment; The second renovation process solvent wash needs the time long, and effect is unsatisfactory.
CN1145279A discloses a kind of method adopting aqueous hydrogen peroxide solution to carry out regenerated from washing, the method adopts the regeneration condition of hydrogenperoxide steam generator concentration 1-45wt%, wash temperature 40-120 DEG C, during preferred regeneration temperature more than 100 DEG C, good regeneration effect can be reached, there is quick, simple feature.But the subject matter that the method exists is that under high temperature, hydrogen peroxide very easily decomposes, and causes hydrogen peroxide utilization ratio greatly to reduce.Meanwhile, the method needs lot of energy equally.
The disclosed method adopting the regeneration of methyl alcohol high-temperature wash of USP6878836B2, be carry out methanol wash with the wash temperature of more than 100 DEG C to deactivator, regenerative agent can use for a long time, and the selective of regenerative agent improves greatly.By improving reaction temperature and keep reaction pressure constant, the selective of constant hydrogen peroxide conversion and product can be obtained.Mainly energy consumption is higher to adopt the method Problems existing, and regeneration effect is unsatisfactory simultaneously.
CN1461671A discloses a kind of renovation process of titanium-containing catalyst, is to process decaying catalyst in the acid solution of pH≤3, then dry and roasting.Described acid solution is the mixed liquor of inorganic acid and hydrogen peroxide, the concentration 0-10wt% of hydrogen peroxide in mixed liquor.
CN101455981A discloses a kind of renovation process of titanium-containing catalyst of improvement, it is characterized in that the method comprises the mixed solution process of titanium-containing catalyst aqueous hydrogen peroxide solution by inactivation and organic acidity compound, then adopt the step of high-temperature vapor or the process of high temperature organic solvent.
CN1302693A discloses a kind of renovation process of titaniferous deactivated zeolite catalyst, specifically, is deposit in case by decaying catalyst at inorganic fluoride, processes in water-bearing media with hydrogen peroxide, the method for heat-treating subsequently.
CN101237928A discloses a kind of method that titanium-containing molecular sieve catalyst is regenerated, specifically a kind of method being used in the titanium-containing molecular sieve catalyst regeneration of alkene epoxidation by using the mixed solvent comprising aqueous hydrogen peroxide solution and alcohol to carry out simple process.
Summary of the invention
The object of this invention is to provide a kind of renovation process of titanium-containing catalyst, before adopting the method to regenerate the specific activity process of the titanium-containing catalyst obtained, activity significantly improves.
The present inventor experimental studies have found that through a large amount of, when the titanium-containing catalyst regeneration to inactivation, successively adopt the titanium-containing catalyst of faintly acid aqueous hydrogen peroxide solution and alkaline substance solution process inactivation, the titanium-containing catalyst activity that regeneration can be made to obtain significantly improves, and the relative crystallinity of titanium-containing catalyst after regeneration and micropore specific area can recover substantially completely, and find further, the faintly acid aqueous hydrogen peroxide solution of low concentration is used in processing procedure, under identical treatment temperature and time, effective compared with highly acid aqueous hydrogen peroxide solution than high concentration, and the method is particularly suitable for the reversibly inactivated situation with carrying out in-situ regeneration of catalyst generation.Based on this, complete the present invention.
For realizing aforementioned object, the invention provides a kind of renovation process of titanium-containing catalyst, wherein, the method comprises: the titanium-containing catalyst of inactivation and aqueous hydrogen peroxide solution are carried out first and contacts, obtain the first mixture; Described first mixture and alkaline substance solution are carried out second contact.
According to the titanium-containing catalyst of method regeneration of deactivated of the present invention, the relative crystallinity of the titanium-containing catalyst after regenerating and micropore specific area can be made to recover substantially completely, and before the titanium-containing catalyst specific activity process after regeneration, activity significantly improves.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of renovation process of titanium-containing catalyst, wherein, the method comprises: the titanium-containing catalyst of inactivation and aqueous hydrogen peroxide solution are carried out first and contacts, obtain the first mixture; Described first mixture and alkaline substance solution are carried out second contact.
In the present invention, described first mixture can for not carrying out the first mixture that any subsequent treatment steps such as (such as filter) washings obtains after carrying out the first contact, also can be carry out after the first contact filtering, wash, solid matter that drying and other steps obtains.
According to the present invention, according to preceding solution, first titanium-containing catalyst is contacted with aqueous hydrogen peroxide solution, and then to contact with alkaline substance solution and carry out regeneration and can well realize object of the present invention, described aqueous hydrogen peroxide solution, the range of choices of alkaline substance solution consumption is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferred described aqueous hydrogen peroxide solution, the consumption mass ratio of alkaline substance solution and titanium-containing catalyst is 0.2-1000:0.2-1000:1, be more preferably 0.3-500:0.3-500:1, more preferably 0.3-50:0.5-40:1, further be preferably 0.3-10:0.3-10:1, specifically can adjust according to needs.
According to one of the present invention preferred embodiment, preferably described first contact contacts with described second the way of contact being incipient impregnation, the consumption of aqueous hydrogen peroxide solution like this, alkaline substance solution is minimum, and follow-up recovery process can be saved, such as without the need to isolated by filtration, washing and directly can carry out drying or roasting, thus eliminate the operations such as filtration, washing, also discharge without washes, significantly reduce the pollution to environment, so not only save operation, and the activation recovering effect of titanium-containing catalyst might as well.
In the present invention, when the first contact contacts as incipient impregnation with second, the consumption mass ratio of aqueous hydrogen peroxide solution, alkaline substance solution and titanium-containing catalyst is generally 0.3-2:0.3-2:1.
According to the present invention, carry out regeneration according to preceding solution and can well realize object of the present invention, and the present inventor is in the favorite outer discovery of research process, method of the present invention is adopted to regenerate, the titanium-containing catalyst of the faintly acid aqueous hydrogen peroxide solution process inactivation of low concentration is used in process, under identical treatment temperature and time, more effective than the highly acid aqueous hydrogen peroxide solution of high concentration, this point is different from existing understanding.Therefore, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the concentration of preferred described aqueous hydrogen peroxide solution is 0.1-5 quality %, is preferably 0.2-2 quality %.
According to the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the pH value of preferred described aqueous hydrogen peroxide solution is 3-6, is preferably 4-5.Wherein, the inorganic bases such as inorganic acid and ammoniacal liquor etc. such as acid-base material example hydrochloric acid can be utilized as required to adjust the pH value of aqueous hydrogen peroxide solution, and this is well known to those skilled in the art, and does not repeat herein.
According to the present invention, carry out regeneration according to preceding solution and can well realize object of the present invention, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the concentration of preferred described alkaline substance solution is 0.01-20 quality %, is more preferably 0.05-10 quality %.
According to the present invention, the alkaline substance solution meeting aforementioned claim all can well realize object of the present invention, the range of choices of the alkaline matter in described alkaline substance solution and the kind of solvent is wider, and described alkaline matter can for the conventional various alkali that can be dissolved in water.
For the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferred described alkaline matter is one or more in ammonia, alkali-metal hydroxide, the hydroxide of alkaline-earth metal, quaternary ammonium base and organic amine (comprising alkylamine, hydramine etc.) compound, more preferably ammonia and/or alcohol amine compound.
In the present invention, preferred described quaternary ammonium base has following formula structure:
r in formula
1, R
2, R
3, R
4be selected from separately as C
1-C
20straight or branched alkyl, C
3-C
20cycloalkyl or C
6-C
20aryl, preferably, R
1, R
2, R
3and R
4be C separately
1-C
10straight chained alkyl, C
3-C
10branched alkyl or C
3-C
10cycloalkyl.Further preferably, R
1, R
2, R
3and R
4be C separately
1-C
6straight chained alkyl or C
3-C
6branched alkyl.The example of described quaternary ammonium base can include but not limited to as TPAOH (comprising four n-pro-pyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetraethyl ammonium hydroxide, TMAH and TBAH (comprising 4-n-butyl ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide).
In the present invention, preferred described organic amine compound is aliphatic hydramine and/or alkylamine, is preferably C
2-C
8aliphatic hydramine (specifically can include but not limited to as MEA, diethanol amine and triethanolamine etc.) and C
2-C
8alkylamine (specifically can include but not limited to as ethamine, propylamine and isomers thereof, butylamine and isomers, butanediamine etc.), be preferably C
2-C
3aliphatic hydramine, be preferably triethanolamine.
In the present invention, preferred described alkali-metal hydroxide is potassium hydroxide and/or NaOH.
In the present invention, the hydroxide barium hydroxide of preferred described alkaline-earth metal and/or calcium hydroxide.
In the present invention, described alkaline matter is ammonia and/or triethanolamine more preferably.
As previously mentioned, the range of choices of the solvent in alkaline substance solution described in the present invention is wider, for the present invention, be preferably in water, alcohol, ketone, ether and ester one or more, be more preferably water and/or alcohol, wherein, alcohol is preferably the monohydric alcohol of C1-C8, the more preferably monohydric alcohol of C1-C4, most preferably be in methyl alcohol, ethanol, the tert-butyl alcohol and isopropyl alcohol one or more.
In the present invention, the range of choices of the temperature of described first contact is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferably the temperature of described first contact is below 100 DEG C, be preferably room temperature to 100 DEG C, be more preferably 50-100 DEG C, be particularly preferably 40-90 DEG C.
In the present invention, the range of choices of the time of described first contact is very wide, specifically can select according to needs, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferably the time of described first contact is at more than 0.5h, is preferably 0.5-72h, is more preferably 1-12h.
In the present invention, the range of choices of the temperature of described second contact is wider, and for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the temperature of preferably described second contact, below 200 DEG C, is preferably 50-180 DEG C.
In the present invention, the range of choices of the time of described second contact is very wide, specifically can select according to needs, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the time of preferably the second contact, at more than 0.1h, is preferably 0.2-12h.
According to the present invention, carry out regeneration according to preceding solution and can well realize object of the present invention, and the present inventor is in the favorite outer discovery of research process, method of the present invention is adopted to regenerate, if described first mixture is successively contacted can improve the performance regenerating the titanium-containing catalyst obtained further with different alkaline substance solution, particularly first described first mixture is contacted with alkaline substance solution, then contact with the alcoholic solution of alkaline matter and can greatly improve the performance regenerating the titanium-containing catalyst obtained, therefore, for the present invention, preferably described first mixture and alkaline substance solution are carried out second to contact and carry out as follows: first described first mixture is contacted with alkaline substance solution, then contact contacting the mixture obtained with the alcoholic solution of alkaline matter again.
In the present invention, the range of choices of the alcoholic solution consumption of described alkaline substance solution, alkaline matter is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the alcoholic solution of preferred described alkaline substance solution, alkaline matter and the consumption mass ratio of titanium-containing catalyst are 0.15-500:0.15-500:1, be preferably 0.2-50:0.5-100:1, be more preferably 0.5-20:0.5-20:1.
According to method of the present invention, the range of choices of described alkaline substance solution kind is wider, for the present invention, in order to further improve the performance regenerating the titanium-containing catalyst obtained, the concentration of preferred described alkaline substance solution is 0.05-10 quality %, is preferably 0.5-5 quality %.
According to method of the present invention, the range of choices of the alcoholic solution kind of described alkaline matter is wider, for the present invention, in order to further improve the performance regenerating the titanium-containing catalyst obtained, the concentration of the alcoholic solution of preferred described alkaline matter is 0.1-20 quality %, be more preferably 0.2-10 quality %, more preferably 0.1-2 quality %.
According to method of the present invention, the range of choices of the temperature that described first mixture contacts with alkaline substance solution is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferably the temperature that contacts with alkaline substance solution of described first mixture is below 200 DEG C, is preferably 50-180 DEG C.
According to method of the present invention, the range of choices of the time that described first mixture contacts with alkaline substance solution is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferably time of contacting with alkaline substance solution of described first mixture is at more than 0.1h, be preferably 0.2-12h, more preferably 0.5-8h.
According to method of the present invention, the range of choices of the temperature contacted with the alcoholic solution of alkaline matter by the mixture that contact obtains is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferably will contact temperature that the mixture that obtains contacts with the alcoholic solution of alkaline matter below 200 DEG C, more preferably 50-150 DEG C.
According to method of the present invention, the range of choices of the time contacted with the alcoholic solution of alkaline matter by the mixture that contact obtains is wider, for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, the time preferably contacted with the alcoholic solution of alkaline matter by the mixture that contact obtains is at more than 0.1h, be more preferably 0.2-10h, more preferably 0.5-8h.
According to method of the present invention, the range of choices of the alcoholic solvent of the alcoholic solution of described alkaline matter is wider, for the present invention, in order to improve the performance of titanium-containing catalyst regenerating and obtain further, the alcoholic solvent of the alcoholic solution of preferred described alkaline matter be selected from methyl alcohol, ethanol, the tert-butyl alcohol and isopropyl alcohol one or more.
According to method of the present invention, as previously mentioned, the range of choices of the kind of described alkaline matter is wider, and for the present invention, in order to improve the performance regenerating the titanium-containing catalyst obtained further, preferred described alkaline matter is selected from ammonia and/or triethanolamine.
According to method of the present invention, preferred method of the present invention also comprises: contact the second mixture obtained by second and carry out filtering, wash and obtain solid, described solid is carried out drying.
According to method of the present invention, filter, washing, these processes dry are familiar with by those skilled in the art, have no special requirements at this, the general distilled water that adopts at normal temperatures and pressures of such as washing rinses repeatedly, and dry run can be carried out at the temperature between room temperature to 200 DEG C.
Method of the present invention, without the need to through highly energy-consuming processes such as roastings, economizes on resources, and environmental friendliness.
According to method of the present invention, the range of choices of the titanium-containing catalyst of described inactivation is wider, and the titanium-containing catalyst of every inactivation all can adopt method of the present invention to regenerate, and method of the present invention is particularly suitable for the regeneration of the titanium-silicon molecular sieve catalyst of inactivation.
Method provided by the invention is applicable to various types of deactivated titanium silicon molecular sieve, as common titanium-silicon molecular sieve TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve etc., the deactivated titanium silicon molecular sieve regenerated through method of the present invention can have its oxidation activity of efficient recovery.
According to method of the present invention, the source of the titanium-containing catalyst of described inactivation is unrestricted, the titanium-containing catalyst of every inactivation all can adopt method of the present invention to regenerate, for the present invention, the titanium-containing catalyst of preferred described inactivation comes from epoxidation reaction of olefines, arene hydroxylation reaction, ketone oxamidinating reaction, the oxidation reaction of alcohol or oxidation of alkanes reaction.Namely renovation process provided by the invention may be used for processing alkene epoxidation, arene hydroxylation, ketone oxamidinating, the oxidation of alcohol or oxidation of alkanes reaction, after a period of time running, such as, occur the titanium-containing catalyst of deactivation phenomenom (as conversion ratio or selectively decrease beyond 2%) in epoxidation of propylene, phenol hydroxylation, cyclohexanone oxamidinating reaction.Even the titanium-containing catalyst of the inactivation adopting existing in-situ regeneration technical finesse means effect undesirable, as catalyst activity but do not made to return to the titanium-containing catalyst of the inactivation of acceptable level through the regeneration such as solvent wash process, method provided by the invention is adopted to carry out regenerating and also can obtain satisfied activation recovering effect.Processing method provided by the invention is particularly useful for the titanium-containing catalyst of propylene ring oxidation reaction inactivation.
Renovation process provided by the invention, simple and easy to do, catalyst activity after regeneration obtains and effectively recovers, and the consumption of various regenerative agent is low and cheap and easy to get in the method processing procedure, when particularly adopting incipient impregnation process, without isolated by filtration, eliminate the operations such as filtration, washing, also without washes discharge, greatly reduce the pollution to environment, significantly improve the environmental and social benefits of regenerative process.
Below by embodiment, the invention will be further described, but therefore do not limit content of the present invention.
In the present invention, in comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.The relative crystallinity RC of sample be carry out on Siemens D5005 type x-ray diffractometer sample X-ray diffraction (XRD) measure, radiographic source be CuK α (
), be that the ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak between 22.5 °-25.0 ° is to represent the degree of crystallinity of sample relative to authentic specimen at 2 θ with sample and authentic specimen, in the present invention, with the sample of comparative example 1 for authentic specimen, its value counts 100%.The micropore specific area data of sample measure on the static n2 absorption apparatus of the ASAP2405 of Micromeritics company of the U.S., and the data such as the relative crystallinity RC of each sample and micropore specific area are in table 1.
In embodiment and comparative example, the pH value of acid aqueous hydrogen peroxide solution used as required by adding hydrochloric acid or ammoniacal liquor realizes (and through test, add different materials and regulate the pH value of aqueous hydrogen peroxide solution substantially not affect the result of reaction) in commercially available aqueous hydrogen peroxide solution.The PX-PH281 type high accuracy pen type acidometer being determined at the production of Guangzhou Pu Xitong Instrument Ltd. of pH value carries out, and the pH value of concrete acid aqueous hydrogen peroxide solution refers to each embodiment and comparative example.
Preparation embodiment 1
This prepares embodiment for preparing the process of TS-1 sieve sample by the method described in " Zeolites, 1992, Vol.12:943-950 ".
22.5g tetraethyl orthosilicate is mixed with 7.0g TPAOH, and add 59.8g distilled water, at normal pressure and 60 DEG C, 1.0h is hydrolyzed after mixing, then add the solution be made up of 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol under agitation, gained mixture is stirred 3h at 75 DEG C, obtains clear colloid, this colloid is put into stainless steel sealed reactor, at 170 DEG C, constant temperature places 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and at 110 DEG C dry 60 minutes, then at 550 DEG C roasting 3h, obtain TS-1 molecular sieve XX-1.
Comparative example 1
This comparative example illustrates the process of HTS inactivation and roasting regeneration in phenol hydroxylation reaction.
TS-1 molecular sieve XX-1 sample prepared by preparation embodiment 1 is used for phenol hydroxylation reaction, and the mol ratio of phenol and hydrogen peroxide is 3:1, take acetone as solvent, at 80 DEG C, react 4h, catalyst is separated from reaction system, dry, 550 DEG C of roasting 3h, be used further to next round reaction, so circulation 5 rear catalyst activity are reduced to original about 80%, by catalyst separation, dry, then through 550 DEG C of roasting 3h, obtain the regeneration sample after roasting, be designated as BS-1.
Comparative example 2
This comparative example illustrates the process of HTS inactivation and roasting regeneration in cyclohexanone oxamidinating reaction.
TS-1 molecular sieve XX-1 sample prepared by preparation embodiment 1 is placed in 100mL to be with in the slurry bed reactor of continuous feed and membrane separation device, add with the speed of 5.7mL/h the mixture (volume ratio of water and hydrogen peroxide is for 10:9) that water and concentration are the aqueous hydrogen peroxide solution of 30 quality % under stirring, the mixture (volume ratio of cyclohexanone and the tert-butyl alcohol is for 1:2.5) of cyclohexanone and the tert-butyl alcohol is added with the speed of 10.5mL/h, the ammoniacal liquor that concentration is 25 quality % is added with the speed of 5.7mL/h, above-mentioned three bursts of material flow are for add simultaneously, simultaneously with corresponding speed continuous discharge, reaction temperature maintains 80 DEG C, every 12h, product sampling chromatogram is analyzed after stable reaction, through after a while, after cyclohexanone conversion ratio drops to 50% by initial 95%, namely catalyst activity reduction about 50%, isolates catalyst, and dry postscript is SH-1,
SH-1 sample roasting regeneration mode is regenerated (by sample SH-1 at 570 DEG C in air atmosphere roasting 4h, obtain roasting regeneration sample, sample is designated as BS-2).
Comparative example 3
This comparative example illustrates the regenerative process of the HTS of inactivation in cyclohexanone oxamidinating reaction.
By the method process that the HTS SH-1 of the inactivation of comparative example 2 describes according to the embodiment 1 of CN1461671A, the catalyst after regeneration is designated as BS-3;
Concrete processing procedure is as follows: the dust technology being 5 quality % by 9 grams of SH-1 samples and 180 grams of concentration mixes, stir 2 hours at 85 DEG C, then filter and obtain solid, solid deionized water is rinsed repeatedly, last at 120 DEG C after drying, roasting 6 hours at 560 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst BS-3.
Comparative example 4
This comparative example illustrates the process that the HTS of propylene ring oxidation reaction inactivation regenerates with method of roasting.
The TS-1 molecular sieve XX-1 getting the preparation of preparation embodiment 1 is placed in 100mL and is with in the slurry bed reactor of continuous feed and membrane separation device, add with the speed of 50mL/h the mixture (mass ratio of methyl alcohol and hydrogen peroxide is for 10:1) that methyl alcohol and concentration are the aqueous hydrogen peroxide solution of 30 quality % under stirring, propylene is added with the speed of 10mL/h, above-mentioned material flow is for add simultaneously, and with corresponding speed continuous discharge, reaction temperature maintains 40 DEG C, pressure maintains 2MPa, analyzes after stable reaction every 12h to product sampling chromatogram.Through after a while, hydrogen peroxide conversion isolates catalyst after dropping to 80% by initial 95%, and dry postscript is SH-2;
SH-2 sample roasting regeneration mode is regenerated (by sample SH-2 at 570 DEG C in air atmosphere roasting 4h), obtain roasting regeneration sample, sample is designated as BS-4, then for phenol hydroxylation reaction in.
Comparative example 5
This comparative example illustrates the regenerative process of the HTS of inactivation in propylene ring oxidation reaction.
By the method process that SH-2 describes according to CN1461671A embodiment 1.Concrete processing procedure is as follows: the dust technology being 5 quality % by 9 grams of SH-2 samples and 180 grams of concentration mixes, and stirs 2 hours at 85 DEG C, filters, solid deionized water is rinsed repeatedly, after 120 DEG C of dryings, roasting 6 hours at 560 DEG C, obtains regeneration titanium-silicon molecular sieve catalyst BS-5.
Comparative example 6
Under normal pressure, 80 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=3, concentration is 10 quality %) mix with deactivated titanium silicon molecular sieve (SH-2) and contact 2.5h, wherein, deactivated titanium silicon molecular sieve (SH-2) is 1:10 with the weight ratio of acid aqueous hydrogen peroxide solution used, then dry after products therefrom filtration washing 120 minutes at 150 DEG C, obtain regeneration titanium-silicon molecular sieve catalyst BS-6.
Comparative example 7
Adopt the method identical with comparative example 6 to carry out acid aqueous hydrogen peroxide solution process to deactivated titanium silicon molecular sieve (SH-2), unlike its pH=5 of acid aqueous hydrogen peroxide solution, mass concentration is 1.0%), obtain regeneration titanium-silicon molecular sieve catalyst BS-7.
Embodiment 1
(dry step is not comprised) after adopting the method identical with comparative example 6 to carry out acid aqueous hydrogen peroxide solution process to deactivated titanium silicon molecular sieve (SH-2), under 80 DEG C and normal pressure, be that the ammonia spirit of 1 quality % contacts 1h again with concentration, wherein, the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:3, then dry after products therefrom filtration washing 120 minutes at 150 DEG C, obtain regeneration titanium-silicon molecular sieve catalyst A.
Embodiment 2
(dry step is not comprised) after adopting the method identical with comparative example 6 to carry out acid aqueous hydrogen peroxide solution process to deactivated titanium silicon molecular sieve (SH-2), under 80 DEG C and normal pressure, be that the methanol solution of the ammonia of 1 quality % contacts 1h again with concentration, wherein, the weight ratio of the methanol solution of deactivated titanium silicon molecular sieve and ammonia is 1:3, then dry after products therefrom filtration washing 120 minutes at 150 DEG C, obtain regeneration titanium-silicon molecular sieve catalyst B.
Embodiment 3
(dry step is not comprised) after adopting the method identical with comparative example 6 to carry out acid aqueous hydrogen peroxide solution process to deactivated titanium silicon molecular sieve (SH-2), under 80 DEG C and normal pressure, the ammonia spirit being first 1 quality % with concentration contacts 1h, wherein, the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:3, then by products therefrom at 50 DEG C, be that the methanol solution of the ammonia of 1 quality % contacts 1h again with concentration, wherein, the weight ratio of the methanol solution of deactivated titanium silicon molecular sieve and ammonia is 1:3, finally dry after products therefrom filtration washing 120 minutes at 150 DEG C, obtain regeneration titanium-silicon molecular sieve catalyst C.
Embodiment 4
(dry step is not comprised) after adopting the method identical with comparative example 7 to carry out acid aqueous hydrogen peroxide solution process to deactivated titanium silicon molecular sieve (SH-2), under 80 DEG C and normal pressure, by the mixture obtained with mass concentration be again 1% ammonia spirit contact 1h, then at 100 DEG C, be that the methanol solution of the ammonia of 1% contacts 1h again with mass concentration, wherein, the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:3, the weight ratio of the methanol solution of deactivated titanium silicon molecular sieve and ammonia is 1:5, finally dry after products therefrom filtration washing 120 minutes at 150 DEG C, obtain the titanium-silicon molecular sieve catalyst D after processing.
Embodiment 5
At normal pressure, under 60 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=4, concentration is 0.5 quality %) mix with deactivated titanium silicon molecular sieve (SH-2) and contact 8h, then at 50 DEG C, be that the potassium hydroxide aqueous solution of 1 quality % contacts 1h again with concentration, then at 150 DEG C, be that the methanol solution of the barium hydroxide of 0.5 quality % mixes and contacts 2.5h again with concentration, wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:5, the weight ratio of the aqueous solution of deactivated titanium silicon molecular sieve and alkali is 1:5, the weight ratio of deactivated titanium silicon molecular sieve and alkali alcosol used is 1:10, then dry after products therefrom filtration washing 240 minutes at 135 DEG C, obtain the titanium-silicon molecular sieve catalyst E after processing.
Embodiment 6
Under normal pressure, 90 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=5, concentration is 2.0 quality %) mix with deactivated titanium silicon molecular sieve (SH-2) and contact 10h, then at 180 DEG C, the ammonia spirit being 0.1 quality % with concentration contacts 5h, then at 60 DEG C, then mix with the ethanolic solution that concentration is 0.2 quality % ammonia and contact 1.5h.Wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:4, and the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:10, and the weight ratio of the alcoholic solution of deactivated titanium silicon molecular sieve and ammonia used is 1:5; Then at 100 DEG C, dry 6h by after products therefrom filtration washing, obtain the titanium-silicon molecular sieve catalyst F after processing.
Embodiment 7
At normal pressure, under 80 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=3, concentration is 0.5 quality %) mix with deactivated titanium silicon molecular sieve (SH-2) and contact 5h, then at 70 DEG C, the aqueous solution being the triethanolamine of 0.5 quality % with concentration contacts 3h, then at 80 DEG C, the ethanolic solution being 0.1 quality % triethanolamine with concentration mixes and contacts 1h, wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:3, the weight ratio of the aqueous solution of deactivated titanium silicon molecular sieve and triethanolamine is 1:2, the weight ratio of the ethanolic solution of deactivated titanium silicon molecular sieve and triethanolamine used is 1:2, then dry after products therefrom filtration washing 180 minutes at 175 DEG C, obtain the titanium-silicon molecular sieve catalyst G after processing.
Embodiment 8
Under normal pressure, 40 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=5.5, concentration is 0.15 quality %) mix with deactivated titanium silicon molecular sieve (SH-1) and contact 6h, then at 90 DEG C, be that the ammonia spirit of 2 quality % contacts 2h again with concentration, then at 70 DEG C, then mix with the t-butanol solution that concentration is the ammonia of 0.1 quality % and contact 5h.Wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:20, and the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:8, and the weight ratio of the t-butanol solution of deactivated titanium silicon molecular sieve and ammonia used is 1:8; Then dry after products therefrom filtration washing 120 minutes at 160 DEG C, obtain the titanium-silicon molecular sieve catalyst H after processing.
Embodiment 9
Under normal pressure, 60 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=5, concentration is 0.2 quality %) mix with deactivated titanium silicon molecular sieve (SH-1) and contact 1h, then at 110 DEG C, the ammonia spirit being 5 quality % with concentration contacts 0.5h, then, at 120 DEG C, the ethanolic solution being the ammonia of 1 quality % with concentration mixes and contacts 0.5h; Wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:50, and the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:1, and the weight ratio of the ethanolic solution of deactivated titanium silicon molecular sieve and ammonia used is 1:1; Then products therefrom is directly dried 270 minutes without filter washing at 130 DEG C, obtain the titanium-silicon molecular sieve catalyst I after processing.
Embodiment 10
The method identical with embodiment 9 is adopted to process deactivated titanium silicon molecular sieve (SH-2), unlike, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution is 1:1(incipient impregnation), all the other conditions are all identical.Obtain the titanium-silicon molecular sieve catalyst J after processing.
Embodiment 11
Under normal pressure, 80 DEG C of conditions, by acid aqueous hydrogen peroxide solution (pH=3, concentration is 1.0 quality %) mix with deactivated titanium silicon molecular sieve (SH-2) and contact 5h, then at 150 DEG C, the ammonia spirit being 0.5 quality % with concentration contacts 4h, wherein, the weight ratio of deactivated titanium silicon molecular sieve and acid aqueous hydrogen peroxide solution used is 1:3, and the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:4; Then dry after products therefrom filtration washing 180 minutes in 175 DEG C, obtain the titanium-silicon molecular sieve catalyst K after processing.
Embodiment 12
The method identical with embodiment 10 is adopted to process deactivated titanium silicon molecular sieve (SH-2), unlike, deactivated titanium silicon molecular sieve (condition is identical with embodiment 10) after acid aqueous hydrogen peroxide solution process, at 70 DEG C, the ammonia spirit being 5 quality % with concentration contacts 0.5h, then at 90 DEG C, be that the methanol solution of 1 quality % ammonia mixes and contacts 0.5h again with concentration, wherein, the weight ratio of deactivated titanium silicon molecular sieve and ammonia spirit is 1:0.6, the weight ratio of the methanol solution of deactivated titanium silicon molecular sieve and ammonia used is 1:0.8, and without washing directly in 160 DEG C of dryings 240 minutes, obtain the titanium-silicon molecular sieve catalyst L after processing.
Embodiment 13
Regenerate according to the method for embodiment 12, unlike, working concentration is that the butanediamine aqueous solution of 5 quality % replaces ammoniacal liquor, and working concentration is the methanol solution of the methanol solution replacement ammonia of the 4-n-butyl ammonium hydroxide of 1 quality %, obtains the titanium-silicon molecular sieve catalyst M after processing.
Embodiment 14
Regenerate according to the method for embodiment 12, unlike, the ammonia spirit of use is 10 quality %, and the concentration of the methanol solution of the ammonia of use is 20 quality %, obtains the titanium-silicon molecular sieve catalyst N after processing.
Embodiment 15
Regenerate according to the method for embodiment 12, unlike, deactivated titanium silicon molecular sieve (SH-2) is 120 DEG C with the Contact Temperature of acid aqueous hydrogen peroxide solution, is 40 DEG C with the Contact Temperature of aqueous slkali, obtains the titanium-silicon molecular sieve catalyst O after processing.
Test case
This test case illustrates the molecular sieve-4 A-O that method of the present invention obtains and molecular sieve XX-1, SH-1, SH-2, BS-1-BS-7 that comparative example method obtains effect for the catalytic oxidation of phenol hydroxylation.
According to catalyst sample: phenol: the weight ratio of acetone=1:20:16 mixes in the there-necked flask of a band condenser pipe, be warming up to 80 DEG C, then under stirring according to phenol: the weight ratio of hydrogen peroxide=1:0.39 adds the aqueous hydrogen peroxide solution that concentration is 30 quality %, react 4h at this temperature, products therefrom measures product composition and then calculates phenol conversion on Agilent6890N type gas chromatograph, the results are shown in Table 1, wherein:
Table 1
As can be seen from the data of table 1, method gained regenerated catalyst of the present invention relative crystallinity and micropore specific area compared with control methods gained regenerated catalyst recover substantially, and catalytic performance is more superior.
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 scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. a renovation process for titanium-containing catalyst, is characterized in that, the method comprises: the titanium-containing catalyst of inactivation and aqueous hydrogen peroxide solution are carried out first and contacts, obtain the first mixture; Described first mixture and alkaline substance solution are carried out second contact.
2. renovation process according to claim 1, wherein, the consumption mass ratio of described aqueous hydrogen peroxide solution, alkaline substance solution and titanium-containing catalyst is 0.2-1000:0.2-1000:1, the concentration of described aqueous hydrogen peroxide solution is 0.1-5 quality %, and the concentration of described alkaline substance solution is 0.01-20 quality %.
3. renovation process according to claim 2, wherein, the consumption mass ratio of described aqueous hydrogen peroxide solution, alkaline substance solution and titanium-containing catalyst is 0.3-50:0.5-40:1, the concentration of described aqueous hydrogen peroxide solution is 0.2-2 quality %, and the concentration of described alkaline substance solution is 0.05-10 quality %.
4. according to the renovation process in claim 1-3 described in any one, wherein, the pH value of described aqueous hydrogen peroxide solution is 3-6.
5. according to the renovation process in claim 1-3 described in any one, wherein, described alkaline matter is ammonia and/or triethanolamine, and the solvent in alkaline substance solution is water and/or alcohol.
6. according to the renovation process in claim 1-3 described in any one, wherein, the condition of described first contact comprises: temperature is 50-100 DEG C, and the time is 0.5-72h; The condition of described second contact comprises: temperature is 50-180 DEG C, and the time is 0.2-12h.
7. according to the renovation process in claim 1-3 described in any one, wherein, described first mixture and alkaline substance solution are carried out second to contact and carry out as follows:
First described first mixture being contacted with alkaline substance solution, then contacting contacting the mixture obtained with the alcoholic solution of alkaline matter again.
8. renovation process according to claim 7, wherein, the alcoholic solution of described alkaline substance solution, alkaline matter and the consumption mass ratio of titanium-containing catalyst are 0.15-500:0.15-500:1, the concentration of described alkaline substance solution is 0.05-10 quality %, and the concentration of the alcoholic solution of alkaline matter is 0.1-20 quality %.
9. the renovation process according to claim 7 or 8, wherein,
The condition that described first mixture contacts with alkaline substance solution comprised: temperature is 50-180 DEG C, the time is 0.2-12h;
The condition that the mixture that contact obtains contacts with the alcoholic solution of alkaline matter is comprised: temperature is 50-150 DEG C, and the time is 0.2-10h.
10. the renovation process according to claim 7 or 8, wherein, the alcoholic solvent of the alcoholic solution of described alkaline matter be selected from methyl alcohol, ethanol, the tert-butyl alcohol and isopropyl alcohol one or more, alkaline matter is selected from ammonia and/or triethanolamine.
11. according to the renovation process in claim 1-3 described in any one, and wherein, the method also comprises: contact the second mixture obtained by second and carry out filtering, wash and obtain solid, described solid is carried out drying.
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| CN112675907A (en) * | 2021-01-08 | 2021-04-20 | 中国科学院大连化学物理研究所 | In-situ combined regeneration method of deactivated titanium-silicon molecular sieve catalyst |
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