CN104415743B - Regenerating method of titanium-containing catalyst - Google Patents
Regenerating method of titanium-containing catalyst Download PDFInfo
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- CN104415743B CN104415743B CN201310407445.7A CN201310407445A CN104415743B CN 104415743 B CN104415743 B CN 104415743B CN 201310407445 A CN201310407445 A CN 201310407445A CN 104415743 B CN104415743 B CN 104415743B
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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 is the new hetero-atom molecular-sieve that last century early eighties start to develop.Synthesize at present
There are the ts-1 of mfi type structure, the ts-2 of mel type structure, and there is the ti-mww of larger pore structure etc..This molecular sieve analog is to perhaps
The reaction such as the epoxidation of many organic oxidizing reactions, such as alkene, arene hydroxylation, Ketohexamethylene oximate, oxidation of alcohol has excellent
Selective oxidation performance and higher catalysis activity, they have before good application as redox-type molecular sieve catalyst
Scape.
Ts-1 molecular sieve is formed in the framework of molecular sieve introducing transition metal titanium and having zsm-5 structure
Plant the novel titanosilicate with superior catalytic selective oxidation performance.The catalysis oxidation that ts-1 molecular sieve not only has titanium is made
With, but also there is the shape-selective effect of zsm-5 molecular sieve and excellent stability.Because ts-1 molecular sieve is in the oxidation of Organic substance
In reaction, can be using free of contamination low concentration hydrogen peroxide as oxidant, it is to avoid oxidizing process complex process and pollution ring
The problem in border, it has the unrivaled energy-conservation of conventional oxidation system, economy and an advantages of environment protection, and has good anti-
Answer selectivity, therefore there is great prospects for commercial application.However, generally running a period of time rear catalyst catalytic performance meeting
It is deteriorated, deactivation phenomenom in catalyst.Catalyst is led to introduce during being likely due to synthesis of molecular sieve the reason inactivation
Impurity or byproduct of reaction are gathered in plug-hole etc. in catalyst micropore.
Ep0100119 discloses and a kind of adopts the method to prepare expoxy propane for the molecular sieve containing titanium epoxidation of propylene.Anti-
During answering, HTS easily inactivates, and this method proposes two kinds of regenerative procesies, and one kind is using 550 DEG C of high-temperature roastings,
Another kind is to be washed using solvent used in methanol or course of reaction.Two kinds of regenerative procesies respectively have weak point, and the first is again
Generation method needs through drying in high-temperature roasting procatalyst first, and high-temperature roasting followed by needs to be cooled down, and need to consume a large amount of
Energy and occupancy equipment；The second renovation process solvent washing needs time is long, and effect is unsatisfactory.
Cn1145279a discloses a kind of method carrying out regenerated from washing using aqueous hydrogen peroxide solution, and the method adopted
When hydrogen peroxide solution concentration 1-45wt%, the regeneration condition of wash temperature 40-120 DEG C, preferably more than 100 DEG C of regeneration temperature, permissible
Reach preferable regeneration effect, there is quick, simple feature.But the subject matter that the method exists is, peroxidating under high temperature
Hydrogen is extremely easy in decomposition, and leads to hydrogen peroxide utilization ratio to substantially reduce.Meanwhile, the method equally need to consume big energy.
Usp6878836b2 is disclosed to adopt methanol high-temperature wash regeneration method, is with more than 100 DEG C of wash temperature
Methanol washing is carried out to deactivator, regenerative agent can use for a long time, and the selectivity of regenerative agent greatly improves.Anti- by improving
Answer temperature to keep reaction pressure constant, can get the selectivity of constant hydrogen peroxide conversion and product.Using the method
The problem existing mainly energy consumption is higher, and regeneration effect is unsatisfactory simultaneously.
Cn1461671a discloses a kind of renovation process of titanium-containing catalyst, is to process to lose in the acid solution of ph≤3
Catalyst alive, is then dried and roasting.Described acid solution is the mixed liquor of mineral acid and hydrogen peroxide, peroxide in mixed liquor
Change concentration 0-10wt% of hydrogen.
Cn101455981a discloses a kind of renovation process of improved titanium-containing catalyst it is characterised in that the method includes
The mixed solution of the titanium-containing catalyst aqueous hydrogen peroxide solution of inactivation and organic acidity compound is processed, then adopts high temperature
Vapor or the step of high temperature organic solvent process.
Cn1302693a discloses a kind of renovation process of titaniferous deactivated zeolite catalyst, specifically, is to urge inactivation
Agent, in the presence of inorganic fluoride, is processed with hydrogen peroxide in water-bearing media, subsequently carries out heat treatment
Method.
Cn101237928a discloses one kind and makes titanium-containing molecular sieve catalyst regeneration method, and specifically one kind is passed through
Carry out simple process using the mixed solvent comprising aqueous hydrogen peroxide solution and alcohol and be used in alkene epoxidation containing titanium molecule
Sieve catalyst regeneration method.
Content of the invention
It is an object of the invention to provide a kind of renovation process of titanium-containing catalyst, urged using the titaniferous that the method regeneration obtains
The activity of agent significantly improves than before processing activity.
The present inventor through substantial amounts of experimental studies have found that, in the titanium-containing catalyst regeneration to inactivation, successively
Process the titanium-containing catalyst of inactivation using faintly acid aqueous hydrogen peroxide solution and alkaline substance solution, can make what regeneration obtained to contain
Titanium catalyst activity is greatly improved, and the relative crystallinity of titanium-containing catalyst after regeneration and micropore specific area substantially can be complete
Full recovery, and it has furthermore been found that using the faintly acid aqueous hydrogen peroxide solution of low concentration in processing procedure, process temperature in identical
Under degree and time, better than the stronger acids aqueous hydrogen peroxide solution effect of high concentration, and the method is particularly suitable for catalyst
There is situation that is reversibly inactivated and carrying out in-situ regeneration.Based on this, complete the present invention.
For realizing object defined above, the invention provides a kind of renovation process of titanium-containing catalyst, wherein, the method includes:
The titanium-containing catalyst of inactivation and aqueous hydrogen peroxide solution are carried out first contact, obtain the first mixture；Described first is mixed
Thing carries out second with alkaline substance solution and contacts.
According to the titanium-containing catalyst of method of the present invention regeneration of deactivated, enable to the relative of the titanium-containing catalyst after regeneration
Degree of crystallinity and micropore specific area substantially completely recover, and the titanium-containing catalyst activity after regeneration is greatly improved than before processing activity.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains 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 includes: by the titaniferous catalysis of inactivation
Agent carries out first with aqueous hydrogen peroxide solution and contacts, and obtains the first mixture；By described first mixture and alkaline substance solution
Carry out the second contact.
In the present invention, described first mixture can not carry out any subsequent treatment (such as mistake for after carrying out the first contact
The steps such as filter, washing) carry out after the first mixture of obtaining or the first contact filtering, wash, drying and other steps obtain
Solid matter.
According to the present invention, according to preceding solution, first titanium-containing catalyst is contacted with aqueous hydrogen peroxide solution, then
Contact with alkaline substance solution again and carry out regeneration and can be very good to realize the purpose of the present invention, described aqueous hydrogen peroxide solution, alkali
Property substance solution consumption optional wider range, for the present invention, in order to improve the titanium-containing catalyst that regeneration obtains further
Performance, the consumption mass ratio of preferably described aqueous hydrogen peroxide solution, alkaline substance solution and titanium-containing catalyst is 0.2-1000:
0.2-1000:1, more preferably 0.3-500:0.3-500:1, more preferably 0.3-50:0.5-40:1, still more preferably
For 0.3-10:0.3-10:1, specifically can be adjusted according to needs.
Preferred embodiment, preferably described first contact contacts with described second and the body such as to be one kind according to the present invention
The way of contact of long-pending dipping, such aqueous hydrogen peroxide solution, the consumption minimum of alkaline substance solution, and can save follow-up
Recovery process, for example without filtration separation, washing and can directly be dried or roasting, thus eliminating filtration, washing etc.
Operation, also no washess discharge, significantly reduces the pollution to environment, so not only saves operation, and titaniferous catalysis
The activation recovering effect of agent might as well.
In the present invention, when the first contact contacts as incipient impregnation with second, aqueous hydrogen peroxide solution, alkaline substance solution
It is generally 0.3-2:0.3-2:1 with the consumption mass ratio of titanium-containing catalyst.
According to the present invention, carry out regeneration according to preceding solution and can be very good to realize the purpose of the present invention, and this
Bright inventor has been surprisingly found that in research process, is regenerated using the method for the present invention, during weak using low concentration
Acid aqueous hydrogen peroxide solution processes the titanium-containing catalyst of inactivation, under identical treatment temperature and time, stronger than high concentration
Acid aqueous hydrogen peroxide solution effect is good, and this point is different from existing understanding.Therefore, for the present invention, in order to improve further
Regenerate the performance of the titanium-containing catalyst obtaining, the concentration of preferably described aqueous hydrogen peroxide solution is 0.1-5 mass %, preferably
0.2-2 mass %.
According to the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains, preferably described hydrogen peroxide further
The ph value of aqueous solution is 3-6, preferably 4-5.Wherein it is possible to utilize mineral acid and the ammonia such as acid-base material example hydrochloric acid as needed
Deng inorganic base etc., the ph value of aqueous hydrogen peroxide solution is adjusted, this is well known to those skilled in the art, does not repeat herein.
According to the present invention, carry out regeneration according to preceding solution and can be very good to realize the purpose of the present invention, for this
Invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, the concentration of preferably described alkaline substance solution is
0.01-20 mass %, more preferably 0.05-10 mass %.
According to the present invention, the alkaline substance solution meeting aforementioned claim all can realize the purpose of the present invention well, described
Optional wider range of the species of the alkaline matter in alkaline substance solution and solvent, described alkaline matter can be conventional
The various alkali that can be dissolved in water.
For the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains, preferably described alkaline matter further
Change for ammonia, alkali-metal hydroxide, the hydroxide of alkaline-earth metal, quaternary ammonium base and organic amine (including alkylamine, hydramine etc.)
One or more of compound, more preferably ammonia and/or alcohol amine compound.
In the present invention, preferably described quaternary ammonium base has a formula:
R in formula1、r2、r3、r4It each is selected from as c1-c20Straight or branched alkyl, c3-
c20Cycloalkyl or c6-c20Aryl it is preferable that r1、r2、r3And r4It is respectively c1-c10Straight chained alkyl, c3-c10Side chain
Alkyl or c3-c10Cycloalkyl.It is further preferred that r1、r2、r3And r4It is respectively c1-c6Straight chained alkyl or c3-c6Side chain
Alkyl.The example of described quaternary ammonium base can be including but not limited to: TPAOH (include four n-pro-pyl ammonium hydroxide and
Tetra isopropyl ammonium hydroxide), tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide and TBAH (include tetra-n-butyl
Ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide).
In the present invention, preferably described organic amine compound is aliphatic hydramine and/or alkylamine, preferably c2-c8Fat
Race's hydramine (can be specifically including but not limited to monoethanolamine, diethanolamine and triethanolamine etc.) and c2-c8Alkylamine (tool
Body can be including but not limited to ethamine, propylamine and its isomer, butylamine and its isomer, butanediamine etc.), preferably c2-c3's
Aliphatic hydramine, preferably triethanolamine.
In the present invention, preferably described alkali-metal hydroxide is potassium hydroxide and/or sodium hydroxide.
In the present invention, the hydroxide barium hydroxide of preferably described alkaline-earth metal and/or calcium hydroxide.
In the present invention, described alkaline matter is more preferably ammonia and/or triethanolamine.
As it was previously stated, optional wider range of the solvent in heretofore described alkaline substance solution, for the present invention, excellent
Elect one or more of water, alcohol, ketone, ether and ester, more preferably water and/or alcohol as, wherein, alcohol is preferably the unitary of c1-c8
One or more of the monohydric alcohol of alcohol, more preferably c1-c4, most preferably methanol, ethanol, the tert-butyl alcohol and isopropanol.
In the present invention, optional wider range of the temperature of described first contact, for the present invention, in order to improve again further
The performance of the titanium-containing catalyst that life obtains, the temperature of preferably described first contact, below 100 DEG C, is preferably room temperature to 100 DEG C,
More preferably 50-100 DEG C, particularly preferably 40-90 DEG C.
In the present invention, the optional scope of the time of described first contact is very wide, specifically can be selected according to needs, pin
To the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, the time of preferably described first contact exists
More than 0.5h, preferably 0.5-72h, more preferably 1-12h.
In the present invention, optional wider range of the temperature of described second contact, for the present invention, in order to improve again further
The performance of titanium-containing catalyst that life obtains, the temperature of preferably described second contact below 200 DEG C, preferably 50-180 DEG C.
In the present invention, the optional scope of the time of described second contact is very wide, specifically can be selected according to needs, pin
To the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, time of the preferably second contact 0.1h with
On, preferably 0.2-12h.
According to the present invention, carry out regeneration according to preceding solution and can be very good to realize the purpose of the present invention, and this
Bright inventor has been surprisingly found that in research process, is regenerated using the method for the present invention, if by described first mixture first
Contact the performance that can improve the titanium-containing catalyst that regeneration obtains further afterwards with different alkaline substance solutions, particularly first will
Described first mixture is contacted with alkaline substance solution, then contacts with the alcoholic solution of alkaline matter and can greatly improve regeneration
Described first mixture and alkaline substance solution therefore, for the present invention, are preferably carried out by the performance of the titanium-containing catalyst obtaining
Second contact is carried out as follows: described first mixture is contacted with alkaline substance solution first, then will contact
The mixture arriving is contacted with the alcoholic solution of alkaline matter again.
In the present invention, described alkaline substance solution, optional wider range of the alcoholic solution consumption of alkaline matter, for this
Invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains, preferably described alkaline substance solution, alkaline matter further
The consumption mass ratio of alcoholic solution and titanium-containing catalyst be 0.15-500:0.15-500:1, preferably 0.2-50:0.5-100:1,
More preferably 0.5-20:0.5-20:1.
The method according to the invention, optional wider range of described alkaline substance solution species, for the present invention, in order to
Further improve the performance of the titanium-containing catalyst that regeneration obtains, the concentration of preferably described alkaline substance solution is 0.05-10
Quality %, preferably 0.5-5 mass %.
The method according to the invention, optional wider range of the alcoholic solution species of described alkaline matter, for the present invention, be
Further improve the performance of the titanium-containing catalyst that regeneration obtains, the concentration of the alcoholic solution of preferably described alkaline matter is 0.1-
20 mass %, more preferably 0.2-10 mass %, more preferably 0.1-2 mass %.
The method according to the invention, the optional scope of the temperature that described first mixture is contacted with alkaline substance solution is relatively
Width, for the present invention, in order to improve performance, preferably described first mixture and the alkali of the titanium-containing catalyst that regeneration obtains further
Property material aqueous solution contact temperature below 200 DEG C, preferably 50-180 DEG C.
The method according to the invention, the optional scope of the time that described first mixture is contacted with alkaline substance solution is relatively
Width, for the present invention, in order to improve performance, preferably described first mixture and the alkali of the titanium-containing catalyst that regeneration obtains further
Property material aqueous solution contact time in more than 0.1h, preferably 0.2-12h, more preferably 0.5-8h.
The method according to the invention, will contact the optional of the temperature that the mixture obtaining is contacted with the alcoholic solution of alkaline matter
Contact, for the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, is preferably obtained by wider range
The temperature that mixture is contacted with the alcoholic solution of alkaline matter below 200 DEG C, more preferably 50-150 DEG C.
The method according to the invention, will contact the optional of the time that the mixture obtaining is contacted with the alcoholic solution of alkaline matter
Contact, for the present invention, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, is preferably obtained by wider range
The time that mixture is contacted with the alcoholic solution of alkaline matter is in more than 0.1h, more preferably 0.2-10h, more preferably 0.5-
8h.
The method according to the invention, optional wider range of the alcoholic solvent of the alcoholic solution of described alkaline matter, for this
Bright, in order to improve the performance of the titanium-containing catalyst that regeneration obtains, the alcoholic solvent of the alcoholic solution of preferably described alkaline matter further
Selected from one or more of methanol, ethanol, the tert-butyl alcohol and isopropanol.
The method according to the invention, as it was previously stated, optional wider range of the species of described alkaline matter, for this
Bright, in order to improve the performance of the titanium-containing catalyst that regeneration obtains further, preferably described alkaline matter is selected from ammonia and/or three ethanol
Amine.
With the method for the invention it is preferred to the method for the present invention also includes: the second mixture that the second contact is obtained enters
Row filters, washing obtains solid, and described solid is dried.
The method according to the invention, filters, washs, these processes are dried being familiar with by those skilled in the art, here
And have no special requirements, such as washing is typically rinsed using distilled water at normal temperatures and pressures repeatedly, and dry run can be in room
Temperature is carried out at a temperature of between 200 DEG C.
The method of the present invention needs not move through the highly energy-consuming process such as roasting, economizes on resources, and environmental friendliness.
The method according to the invention, optional wider range of the titanium-containing catalyst of described inactivation, the titaniferous of every inactivation is urged
Agent all can be regenerated using the method for the present invention, method of the invention is particularly suitable for the titanium-silicon molecular sieve catalyst inactivating
Regeneration.
The method that the present invention provides is applied to various types of deactivated titanium silicon molecular sieves, as common HTS ts-
1st, ts-2, ti-beta, ti-mww molecular sieve etc., the deactivated titanium silicon molecular sieve through method of the present invention regeneration can be effectively extensive
Its oxidation activity multiple.
The method according to the invention, the source of the titanium-containing catalyst of described inactivation is unrestricted, and the titaniferous of every inactivation is urged
Agent all can be using method of the present invention regeneration, and for the present invention, the titanium-containing catalyst of preferably described inactivation comes from alkene ring
Oxidation reaction, arene hydroxylation reaction, ketone oxamidinating reaction, the oxidation reaction of alcohol or oxidation of alkanes reaction.I.e. the present invention provides
Renovation process can be used for process alkene epoxidation, arene hydroxylation, ketone oxamidinating, the oxidation of alcohol or oxidation of alkanes reaction,
For example deactivation phenomenom (as turned after operating through a period of time in reacting in epoxidation of propylene, phenol hydroxylation, cyclohexanone oxamidinating
Rate or selectivity decrease beyond 2%) titanium-containing catalyst.Even with existing in-situ regeneration technical finesse means effect not
The preferably titanium-containing catalyst of inactivation, such as but can not make catalyst activity return to through Regeneration Treatment such as solvent washings acceptable
The inactivation of level titanium-containing catalyst, using the present invention provide method carry out regeneration can also obtain satisfied activity
Recovery effects.The processing method that the present invention provides is particularly suited for the titanium-containing catalyst of propylene ring oxidation reaction inactivation.
The renovation process that the present invention provides, simple and easy to do, the catalyst activity after regeneration has obtained effectively recovering, and
In the method processing procedure, the consumption of various regenerative agents is low and cheap and easy to get, when processing especially with incipient impregnation,
No filtration separation, eliminates the operations such as filtration, washing, and also no washess discharge, greatly reduces the pollution to environment, significantly
Improve the environmental and social benefits of regenerative process.
Below by embodiment, the invention will be further described, but and is not so limited present disclosure.
In the present invention, in comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.The relative crystallization of sample
Degree rc is that the x-ray diffraction (xrd) carrying out sample on siemens d5005 type X-ray diffraction instrument measures, and radiographic source is cuk
α (), the diffracted intensity being the five fingers diffractive features peak between 22.5 ° -25.0 ° in 2 θ with sample and authentic specimen
The ratio of (peak height) sum representing the degree of crystallinity that sample is with respect to authentic specimen, in the present invention, with the sample of comparative example 1 as base
Quasi- sample, its value is calculated as 100%.The micropore specific area data of sample is quiet in the asap2405 of micromeritics company of the U.S.
It is measured on state n2 absorption apparatus, the data such as the relative crystallinity rc of each sample and micropore specific area is shown in Table 1.
In embodiment and comparative example, the ph value of acidity aqueous hydrogen peroxide solution used is as desired by toward commercially available mistake
Adding hydrochloric acid or ammonia in oxidation aqueous solution of hydrogen (and through test, adds different materials to adjust aqueous hydrogen peroxide solutions realizing
Ph value have substantially no effect on the result of reaction).The px-ph281 that the mensure of ph value produces in Guangzhou Pu Xitong Instrument Ltd.
Carry out on type high accuracy pen type acidometer, specifically the ph value of acid aqueous hydrogen peroxide solution refers to each embodiment and comparative example.
Preparation embodiment 1
This preparation embodiment is by the method preparation ts-1 described in " zeolites, 1992, vol.12:943-950 "
The process of sieve sample.
22.5g tetraethyl orthosilicate is mixed with 7.0g TPAOH, and adds 59.8g distilled water, mixing is all
Even hydrolysis 1.0h at normal pressure and 60 DEG C, then adds by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol under agitation
The solution being formed, gained mixture is stirred 3h at 75 DEG C, obtains clear colloid, this colloid is put into rustless steel close
Envelope reactor, at 170 DEG C, constant temperature is placed 3 days, obtains the mixture of crystallization product；This mixture is filtered, washes with water, and
It is dried 60 minutes at 110 DEG C, roasting 3h at 550 DEG C, obtain ts-1 molecular sieve xx-1.
Comparative example 1
The process of the explanation of this comparative example 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, phenol and hydrogen peroxide
Mol ratio be 3:1, with acetone as solvent, at 80 DEG C react 4h, by catalyst from reaction system separate, be dried, 550 DEG C
Roasting 3h, is used further to next round reaction, so circulates 5 rear catalyst activity and is reduced to original 80% about, catalyst is divided
From, dry, it is then passed through 550 DEG C of roasting 3h, obtain the regeneration sample after roasting, be designated as bs-1.
Comparative example 2
The process of the explanation of this comparative example 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 band continuous feed and membrane separation device
Slurry bed reactor in, under stirring, water is added with the speed of 5.7ml/h and aquae hydrogenii dioxidi that concentration is 30 mass %
The mixture (volume ratio of water and hydrogen peroxide is 10:9) of solution, adds Ketohexamethylene and the tert-butyl alcohol with the speed of 10.5ml/h
Mixture (volume ratio of Ketohexamethylene and the tert-butyl alcohol is 1:2.5), adds, with the speed of 5.7ml/h, the ammonia that concentration is 25 mass %,
Above-mentioned three strands of material streams are to be simultaneously introduced, and simultaneously with corresponding speed continuous discharge, reaction temperature maintains 80 DEG C, stable reaction
Every 12h, product sampling chromatograph is analyzed afterwards；Through after a while, Ketohexamethylene conversion ratio is dropped to by initial 95%
After 50%, i.e. catalyst activity reduction 50% about, isolate catalyst, it is sh-1 that postscript is dried；
Sh-1 sample roasting regeneration mode is regenerated (by sample sh-1 at 570 DEG C roasting 4h in air atmosphere, obtain
Roasting regeneration sample, sample is designated as bs-2).
Comparative example 3
The regenerative process of this comparative example explanation HTS of inactivation in cyclohexanone oxamidinating reaction.
The HTS sh-1 of the inactivation of comparative example 2 is processed according to the method that the embodiment 1 of cn1461671a describes,
Catalyst after regeneration is designated as bs-3；
Concrete processing procedure is as follows: the dust technology that 9 grams of sh-1 samples and 180 grams of concentration are 5 mass % is mixed, in 85 DEG C
Lower stirring 2 hours, is then filtrated to get solid, solid deionized water is rinsed repeatedly, after being dried at 120 DEG C, in
Roasting 6 hours at 560 DEG C, obtain 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 is regenerated with method of roasting.
The ts-1 molecular sieve xx-1 taking preparation embodiment 1 preparation is placed in the silt with continuous feed and membrane separation device for the 100ml
In slurry bed reactor, under stirring, methanol is added with the speed of 50ml/h and hydrogen peroxide that concentration is 30 mass % is water-soluble
The mixture (methanol is 10:1 with the mass ratio of hydrogen peroxide) of liquid, adds propylene with the speed of 10ml/h, above-mentioned material stream is
It is simultaneously introduced, and with corresponding speed continuous discharge, reaction temperature maintains 40 DEG C, and pressure maintains 2mpa, after stable reaction
Every 12h, product sampling chromatograph is analyzed.Through after a while, hydrogen peroxide conversion is dropped to by initial 95%
After 80%, isolate catalyst, it is sh-2 that postscript is dried；
Sh-2 sample roasting regeneration mode is regenerated (will sample sh-2 roasting in air atmosphere at 570 DEG C
4h), obtain roasting regeneration sample, sample is designated as bs-4, be subsequently used in phenol hydroxylation reaction.
Comparative example 5
The regenerative process of this comparative example explanation HTS of inactivation in propylene ring oxidation reaction.
Sh-2 is processed according to the method that cn1461671a embodiment 1 describes.Concrete processing procedure is as follows: by 9 grams of sh-2
Sample is mixed with the dust technology that 180 grams of concentration is 5 mass %, stirs 2 hours at 85 DEG C, filters, solid deionized water is repeatedly
Rinse, after 120 DEG C of dryings, roasting 6 hours at 560 DEG C, obtain regeneration titanium-silicon molecular sieve catalyst bs-5.
Comparative example 6
Under the conditions of normal pressure, 80 DEG C, by acid aqueous hydrogen peroxide solution (ph=3, concentration is 10 mass %) and deactivated titanium silicon
Molecular sieve (sh-2) mixing contact 2.5h, wherein, deactivated titanium silicon molecular sieve (sh-2) and acidity aqueous hydrogen peroxide solution used
Products therefrom filtration washing for 1:10, is then dried 120 minutes at 150 DEG C by weight ratio, obtains regenerating HTS
Catalyst bs-6.
Comparative example 7
Using with comparative example 6 identical method, deactivated titanium silicon molecular sieve (sh-2) is carried out at acid aqueous hydrogen peroxide solution
Reason, except for the difference that acid its ph=5 of aqueous hydrogen peroxide solution, mass concentration is 1.0%), obtain regenerating titanium-silicon molecular sieve catalyst
bs-7.
Embodiment 1
Using with comparative example 6 identical method, deactivated titanium silicon molecular sieve (sh-2) is carried out at acid aqueous hydrogen peroxide solution
After reason (step not including drying), under 80 DEG C and normal pressure, then the ammonia spirit being 1 mass % with concentration contacts 1h, wherein,
Products therefrom filtration washing, than for 1:3, is then dried at 150 DEG C by the weight of deactivated titanium silicon molecular sieve and ammonia spirit
120 minutes, obtain regenerating titanium-silicon molecular sieve catalyst a.
Embodiment 2
Using with comparative example 6 identical method, deactivated titanium silicon molecular sieve (sh-2) is carried out at acid aqueous hydrogen peroxide solution
After reason (step not including drying), under 80 DEG C and normal pressure, then the methanol solution of the ammonia being 1 mass % with concentration contacts 1h, its
In, the weight of deactivated titanium silicon molecular sieve and the methanol solution of ammonia than for 1:3, then by products therefrom filtration washing after 150 DEG C
Lower drying 120 minutes, obtains regenerating titanium-silicon molecular sieve catalyst b.
Embodiment 3
Using with comparative example 6 identical method, deactivated titanium silicon molecular sieve (sh-2) is carried out at acid aqueous hydrogen peroxide solution
After reason (step not including drying), under 80 DEG C and normal pressure, the ammonia spirit being first 1 mass % with concentration contacts 1h, wherein,
The weight of deactivated titanium silicon molecular sieve and ammonia spirit ratio for 1:3, then by products therefrom at 50 DEG C, then is 1 mass % with concentration
Ammonia methanol solution contact 1h, wherein, the weight of deactivated titanium silicon molecular sieve and the methanol solution of ammonia ratio for 1:3, finally by institute
Obtain product filtration washing to dry 120 minutes at 150 DEG C, obtain regenerating titanium-silicon molecular sieve catalyst c.
Embodiment 4
Using with comparative example 7 identical method, deactivated titanium silicon molecular sieve (sh-2) is carried out at acid aqueous hydrogen peroxide solution
After reason (step not including drying), under 80 DEG C and normal pressure, the mixture obtaining is again 1% ammonia is molten with mass concentration
Liquid contacts 1h, and then at 100 DEG C, then the methanol solution of the ammonia being 1% with mass concentration contacts 1h, wherein, deactivated titanium silicon molecule
Sieve and the weight of ammonia spirit ratio for 1:3, the weight of deactivated titanium silicon molecular sieve and the methanol solution of ammonia ratio for 1:5, finally by institute
Obtain product filtration washing to dry 120 minutes at 150 DEG C, the titanium-silicon molecular sieve catalyst d after being processed.
Embodiment 5
Under the conditions of normal pressure, 60 DEG C, by acid aqueous hydrogen peroxide solution (ph=4, concentration is 0.5 mass %) and deactivated titanium silicon
Molecular sieve (sh-2) mixing contact 8h, then at 50 DEG C, then the potassium hydroxide aqueous solution being 1 mass % with concentration contacts 1h, connects
At 150 DEG C, then the methanol solution mixing of the barium hydroxide being 0.5 mass % with concentration contacts 2.5h, wherein, deactivated titanium silicon
The weight ratio of molecular sieve and acidity aqueous hydrogen peroxide solution used for 1:5, the weight of deactivated titanium silicon molecular sieve and the aqueous solution of alkali
Than for 1:5, the weight of deactivated titanium silicon molecular sieve and alkali alcosol used is than for 1:10；Then by after products therefrom filtration washing
Dry 240 minutes at 135 DEG C, the titanium-silicon molecular sieve catalyst e after being processed.
Embodiment 6
Under the conditions of normal pressure, 90 DEG C, by acid aqueous hydrogen peroxide solution (ph=5, concentration is 2.0 mass %) and deactivated titanium silicon
Molecular sieve (sh-2) mixing contact 10h, then at 180 DEG C, the ammonia spirit being 0.1 mass % with concentration contacts 5h, then in
At 60 DEG C, then the ethanol solution mixing being 0.2 mass % ammonia with concentration contacts 1.5h.Wherein, deactivated titanium silicon molecular sieve and acid used
Than for 1:4, the weight of deactivated titanium silicon molecular sieve and ammonia spirit is than for 1:10, deactivated titanium silicon for the weight of property aqueous hydrogen peroxide solution
The weight of molecular sieve and the alcoholic solution of ammonia used is than for 1:5；Then products therefrom filtration washing is dried 6h at 100 DEG C,
Titanium-silicon molecular sieve catalyst f after being processed.
Embodiment 7
Under the conditions of normal pressure, 80 DEG C, by acid aqueous hydrogen peroxide solution (ph=3, concentration is 0.5 mass %) and deactivated titanium silicon
Molecular sieve (sh-2) mixing contact 5h, then at 70 DEG C, the aqueous solution of the triethanolamine being 0.5 mass % with concentration contacts 3h,
Then, at 80 DEG C, the ethanol solution being 0.1 mass % triethanolamine with concentration mixing contacts 1h, wherein, deactivated titanium silicon molecular sieve
With the weight ratio of acidity aqueous hydrogen peroxide solution used for 1:3, the weight of deactivated titanium silicon molecular sieve and the aqueous solution of triethanolamine
Than for 1:2, the weight of deactivated titanium silicon molecular sieve and the ethanol solution of triethanolamine used is than for 1:2；Then by products therefrom mistake
Filter washing is dried 180 minutes at 175 DEG C, the titanium-silicon molecular sieve catalyst g after being processed.
Embodiment 8
Under the conditions of normal pressure, 40 DEG C, by acid aqueous hydrogen peroxide solution (ph=5.5, concentration is 0.15 mass %) and inactivation
HTS (sh-1) mixing contact 6h, then at 90 DEG C, then the ammonia spirit being 2 mass % with concentration contacts 2h, then
At 70 DEG C, then the t-butanol solution mixing of the ammonia being 0.1 mass % with concentration contacts 5h.Wherein, deactivated titanium silicon molecular sieve and institute
It is 1:20 with the weight ratio of acid aqueous hydrogen peroxide solution, the weight of deactivated titanium silicon molecular sieve and ammonia spirit ratio for 1:8, inactivates
The weight of HTS and the t-butanol solution of ammonia used is than for 1:8；Then by products therefrom filtration washing at 160 DEG C
Dry 120 minutes, the titanium-silicon molecular sieve catalyst h after being processed.
Embodiment 9
Under the conditions of normal pressure, 60 DEG C, by acid aqueous hydrogen peroxide solution (ph=5, concentration is 0.2 mass %) and deactivated titanium silicon
Molecular sieve (sh-1) mixing contact 1h, then at 110 DEG C, the ammonia spirit being 5 mass % with concentration contacts 0.5h, then in
At 120 DEG C, the ethanol solution mixing of the ammonia being 1 mass % with concentration contacts 0.5h；Wherein, deactivated titanium silicon molecular sieve and acid used
Than for 1:50, the weight of deactivated titanium silicon molecular sieve and ammonia spirit is than for 1:1, deactivated titanium silicon for the weight of property aqueous hydrogen peroxide solution
The weight of molecular sieve and the ethanol solution of ammonia used is than for 1:1；Then by products therefrom without filtration washing directly in 130 DEG C
Lower drying 270 minutes, the titanium-silicon molecular sieve catalyst i after being processed.
Embodiment 10
Using method same as Example 9, deactivated titanium silicon molecular sieve (sh-2) is processed, except for the difference that, inactivate titanium
The weight of si molecular sieves and acid aqueous hydrogen peroxide solution is than for 1:1(incipient impregnation), remaining condition all same.Processed
Titanium-silicon molecular sieve catalyst j afterwards.
Embodiment 11
Under the conditions of normal pressure, 80 DEG C, by acid aqueous hydrogen peroxide solution (ph=3, concentration is 1.0 mass %) and deactivated titanium silicon
Molecular sieve (sh-2) mixing contact 5h, then at 150 DEG C, the ammonia spirit being 0.5 mass % with concentration contacts 4h, wherein, loses
Live HTS with the weight ratio of acidity aqueous hydrogen peroxide solution used for 1:3, deactivated titanium silicon molecular sieve and ammonia spirit
Weight is than for 1:4；Then products therefrom filtration washing is dried 180 minutes after 175 DEG C, the HTS after being processed
Catalyst k.
Embodiment 12
Using method same as in Example 10, deactivated titanium silicon molecular sieve (sh-2) is processed, except for the difference that, losing
Live HTS processes through acid aqueous hydrogen peroxide solution after (condition is same as in Example 10), at 70 DEG C, with concentration be 5
The ammonia spirit contact 0.5h of quality %, then at 90 DEG C, then the methanol solution mixing being 1 mass % ammonia with concentration contacts
0.5h, wherein, the weight of deactivated titanium silicon molecular sieve and ammonia spirit ratio for 1:0.6, the first of deactivated titanium silicon molecular sieve and ammonia used
The weight of alcoholic solution than for 1:0.8 and not scrubbed and direct in 160 DEG C of dryings 240 minutes, the titanium silicon molecule after being processed
Sieve catalyst l.
Embodiment 13
Method according to embodiment 12 is regenerated, and except for the difference that, concentration is the butanediamine aqueous solution generation of 5 mass %
For ammonia, concentration is the methanol solution of the methanol solution replacement ammonia of the 4-n-butyl ammonium hydroxide of 1 mass %, is processed
Titanium-silicon molecular sieve catalyst m afterwards.
Embodiment 14
Method according to embodiment 12 is regenerated, and except for the difference that, the ammonia spirit of use is 10 mass %, the ammonia of use
Methanol solution concentration be 20 mass %, the titanium-silicon molecular sieve catalyst n after being processed.
Embodiment 15
Method according to embodiment 12 is regenerated, except for the difference that, deactivated titanium silicon molecular sieve (sh-2) and acid peroxidating
The Contact Temperature of aqueous solution of hydrogen is 120 DEG C, is 40 DEG C with the Contact Temperature of aqueous slkali, the HTS after being processed is urged
Agent o.
Test case
This test case illustrates the molecular sieve a-o that obtains of the method for the present invention and comparative example method obtains molecular sieve xx-1,
Sh-1, sh-2, bs-1-bs-7 are used for the effect of the catalytic oxidation of phenol hydroxylation.
According to catalyst sample: phenol: the weight of acetone=1:20:16 is more mixed than in a there-necked flask with condensing tube
Close uniformly, be warming up to 80 DEG C, then according to phenol under stirring: the weight of hydrogen peroxide=1:0.39 than addition concentration is
The aqueous hydrogen peroxide solution of 30 mass %, reacts 4h, products therefrom is on agilent6890n type gas chromatograph at this temperature
Measure product composition and then calculate phenol conversion, the results are shown in Table 1, wherein:
Table 1
Method of the present invention gained regenerated catalyst and control methods gained regeneration catalyzing be can be seen that by the data of table 1
Relative crystallinity is compared in agent and micropore specific area recovers substantially, and catalytic performance is more superior.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to the scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (9)
1. a kind of renovation process of titanium-containing catalyst is it is characterised in that the method includes: by the titanium-containing catalyst of inactivation and peroxide
Change aqueous solution of hydrogen and carry out the first contact, the concentration of described aqueous hydrogen peroxide solution is 0.1-5 mass %, obtains the first mixture；
Described first mixture and alkaline substance solution are carried out second contact, wherein,
The concentration of described alkaline substance solution is 0.01-20 mass %；
The temperature of described first contact is 50-100 DEG C；
The temperature of described second contact is 50-180 DEG C；
Described first mixture and alkaline substance solution carried out second contact carrying out as follows:
Described first mixture is contacted with alkaline substance solution first, then by the mixture that obtains of contact again with basic species
The alcoholic solution contact of matter；
The concentration of described alkaline substance solution is 0.05-10 mass %, and the concentration of the alcoholic solution of alkaline matter is 0.1-20 matter
Amount %；
Described alkaline matter is ammonia and/or triethanolamine.
2. renovation process according to claim 1, wherein, described aqueous hydrogen peroxide solution, alkaline substance solution and titaniferous
The consumption mass ratio of catalyst is 0.2-1000:0.2-1000:1.
3. renovation process according to claim 2, wherein, described aqueous hydrogen peroxide solution, alkaline substance solution and titaniferous
The consumption mass ratio of catalyst is 0.3-50:0.5-40:1, and the concentration of described aqueous hydrogen peroxide solution is 0.2-2 mass %, institute
The concentration stating alkaline substance solution is 0.05-10 mass %.
4. the renovation process according to any one in claim 1-3, wherein, the ph value of described aqueous hydrogen peroxide solution is
3-6.
5. the renovation process according to any one in claim 1-3, wherein, the condition of described first contact includes: when
Between be 0.5-72h；The condition of described second contact includes: the time is 0.2-12h.
6. renovation process according to claim 1, wherein, described alkaline substance solution, the alcoholic solution of alkaline matter with
The consumption mass ratio of titanium-containing catalyst is 0.15-500:0.15-500:1.
7. the renovation process according to claim 1 or 6, wherein,
The condition that described first mixture is contacted with alkaline substance solution includes: temperature is 50-180 DEG C, and the time is 0.2-
12h；
The condition that the mixture that obtains of contact is contacted with the alcoholic solution of alkaline matter includes: temperature is 50-150 DEG C, and the time is
0.2-10h.
8. the renovation process according to claim 1 or 6, wherein, the alcoholic solvent of the alcoholic solution of described alkaline matter is selected from first
One or more of alcohol, ethanol, the tert-butyl alcohol and isopropanol.
9. the renovation process according to any one in claim 1-3, wherein, the method also includes: second is contacted
To the second mixture carry out filtering, wash and obtain solid, described solid is dried.
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| CN101439300A (en) * | 2007-11-22 | 2009-05-27 | 中国石油化工股份有限公司 | Regeneration method for deactivated titanium silicon molecular sieve |
| EP1190770B1 (en) * | 1997-07-01 | 2009-08-05 | Lyondell Chemical Technology, L.P. | Process for regenerating epoxidation catalysts |
| CN103182322A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Treatment method of inactivated titanium silicon molecular sieve |
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| EP1190770B1 (en) * | 1997-07-01 | 2009-08-05 | Lyondell Chemical Technology, L.P. | Process for regenerating epoxidation catalysts |
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