CN104014365B - A kind of renovation process of HTS - Google Patents
A kind of renovation process of HTS Download PDFInfo
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- CN104014365B CN104014365B CN201310063152.1A CN201310063152A CN104014365B CN 104014365 B CN104014365 B CN 104014365B CN 201310063152 A CN201310063152 A CN 201310063152A CN 104014365 B CN104014365 B CN 104014365B
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Abstract
A kind of renovation process of HTS, it is characterized in that including by the HTS of inactivation and selected from dimethyl sulfoxide, sulfolane, N methyl pyrrolidone, N, N dimethylformamide and N, at least one compound contact in N dimethyl acetylamide, then by the step of the product after contact with a kind of alkaline solution mixed processing, wherein described contact, at a temperature below the boiling temperature of described compound.
Description
Technical field
The present invention relates to the renovation process of a kind of HTS.
Background technology
HTS be last century early eighties start exploitation novel hetero-atom molecular-sieve.Close at present
The TS-1 having MFI structure become out, the TS-2 of MEL structure, and there is the TS-48 etc. of large hole structure.
This molecular sieve analog is to the many epoxidation of organic oxidizing reaction, such as alkene, arene hydroxylation, cyclohexanone-oximes
Change, the oxidation etc. of alcohol is reacted and is had excellent selective oxidation performance and higher catalysis activity, and they are as oxygen
Change reduced form molecular sieve catalyst to have a good application prospect.
Wherein TS-1 molecular sieve is to be introduced in the framework of molecular sieve with ZSM-5 structure by transition metal titanium
A kind of novel titanosilicate with superior catalytic selective oxidation performance formed.TS-1 not only has
The catalysed oxidn of titanium, but also there is the shape-selective effect of ZSM-5 molecular sieve and excellent stability.By
In TS-1 molecular sieve in organic oxidation reaction, free of contamination low concentration hydrogen peroxide can be used as oxygen
Agent, it is to avoid oxidizing process complex process and pollute the problem of environment, has conventional oxidation system without comparable
Energy-conservation, the economy intended and advantages of environment protection, and there is good reaction selectivity, therefore have greatly
Prospects for commercial application.But, generally after running a period of time, the catalytic performance of HTS can be deteriorated,
Deactivation phenomenom occurs.The impurity or anti-that the reason causing inactivation introduces during being likely due to synthesis of molecular sieve
Answer byproducts accumulation plug-hole etc. in catalyst micropore.
EP0100119 discloses and a kind of uses molecular sieve containing titanium epoxidation of propylene with the method preparing expoxy propane.
In course of reaction, HTS is easy to inactivation, this method proposes two kinds of regenerative procesies, Yi Zhongshi
Using 550 DEG C of high-temperature roastings, another kind is to use the solvent washing used in methanol or course of reaction, and two kinds again
Raw process is respectively arranged with weak point.First the first regeneration need through being dried at high-temperature roasting procatalyst, high temperature
Roasting followed by cools down, and need to consume big energy and take equipment；The second renovation process solvent washs
Require time for long, and effect is unsatisfactory.
USP5620935(CN1145279A) disclose and a kind of use aqueous hydrogen peroxide solution to carry out regenerated from washing
Method, the method uses hydrogenperoxide steam generator concentration 1～45wt%, wash temperature 40～the carded sliver again of 120 DEG C
Part, preferably during regeneration temperature more than 100 DEG C, can reach preferable regeneration effect, have quick, simple
Feature.But the subject matter existed is that under high temperature, hydrogen peroxide is extremely easy in decomposition, hydrogen peroxide is caused to utilize effect
Rate is substantially reduced, and meanwhile, the method need to consume big energy equally.
USP6878836B2 discloses employing methanol high-temperature wash regeneration method, is with the temperature of more than 100 DEG C
Deactivator is carried out methanol washing, and regenerative agent can use for a long time, and the selectivity of regenerative agent is greatly improved.
The method keeps reaction pressure constant by improving reaction temperature, available constant hydrogen peroxide conversion
Selectivity with product.It is higher that the problem existed is mainly energy consumption, and regeneration effect is unsatisfactory simultaneously.
CN1461671A discloses the renovation process of a kind of titanium-containing catalyst, is to locate in the acid flux material of pH≤3
Reason decaying catalyst, is then dried and roasting.What described acid solution was mineral acid with hydrogen peroxide is mixed
Close liquid, the concentration 0～10wt% of hydrogen peroxide in mixed liquor.
CN101602011A discloses the renovation process of a kind of Ti-MWW molecular sieve, is by the titanium silicon molecule of inactivation
Sieve first processes through acid compound solution, then processes through alkaline compound solution, be then passed through filter, washing,
Dry, roasting, obtains the HTS of regeneration.
CN101455981A discloses the renovation process of the titanium-containing catalyst of a kind of improvement, it is characterised in that this side
Method includes at the titanium-containing catalyst aqueous hydrogen peroxide solution of inactivation and the mixed solution of organic acidity compound
Reason, then uses the step that high-temperature vapor or high temperature organic solvent process.
CN1302693A discloses the renovation process of a kind of titaniferous deactivated zeolite catalyst, is by decaying catalyst
In the presence of inorganic fluoride, process with hydrogen peroxide in water-bearing media, carry out subsequently at heat
The method of reason.
CN101237928A discloses one and makes titanium-containing molecular sieve catalyst regeneration method, is comprised by use
The mixed solvent of aqueous hydrogen peroxide solution and alcohol carry out simple process and be used in alkene epoxidation containing titanium molecule
Sieve catalyst regenerates.
Summary of the invention
It is an object of the invention to provide the renovation process of a kind of HTS being different from prior art, save
Energy consumption and cost, and greatly reduce the regenerative process pollution to environment.
The renovation process of the HTS that the present invention provides, it is characterised in that include the titanium silicon molecule of inactivation
Sieve and selected from dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and N, N-
At least one compound contact in dimethyl acetylamide, then by the product after contact and a kind of alkaline solution
The step of mixed processing, wherein described contact, at a temperature below the boiling temperature of described compound.
The renovation process that the present invention provides, relative crystallinity and the micropore specific area of HTS also obtain
Recovering, activity and activity stability are preferable；Dimethyl sulfoxide therein, sulfolane, N-Methyl pyrrolidone,
N,N-dimethylformamide and DMAC N,N' dimethyl acetamide etc. can return in the preferred case after simple separation
With repeatedly, greatly reduce the regenerative process pollution to environment.
Detailed description of the invention
The renovation process of the HTS that the present invention provides, it is characterised in that include the titanium silicon molecule of inactivation
Sieve and selected from dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and N, N-
At least one compound contact in dimethyl acetylamide, then by the product after contact and a kind of alkaline solution
The step of mixed processing, wherein described contact, at a temperature below the boiling temperature of described compound.
In the renovation process that the present invention provides, the HTS of described inactivation, can be the titanium silicon molecule of inactivation
Sieve former powder, it is also possible to be inactivation with HTS as active component, be aided with substrate and binding agent molding obtains
Catalyst.HTS is at organic oxidation reaction such as alkene epoxidation, arene hydroxylation, ketone ammonia
Oximate, the oxidation of alcohol or oxidation of alkanes reaction (such as phenol hydroxylation, cyclohexanone oxamidinating, propylene epoxy
Change) after middle operation a period of time, owing to by-product assembles plugging hole road, bone in micropore at reaction conditions
Frame silicon titanium species changes into non-skeleton species, run off in active center, structure collapse etc., causes catalytic performance to become
, there is deactivation phenomenom in difference.Such as, in phenol hydroxylation reacts, with titanium-silicon molecular sieve TS-1 as catalyst,
Under conditions of the mol ratio of phenol and hydrogen peroxide is 3:1 and 80 DEG C, carry out phenol hydroxylation reaction, catalyst
Without regeneration cycle, recycle phenol conversion after repeatedly and decline (from 25% decline after such as recycling 5 times
To less than 12%), at this point it is possible to think that now this titanium-silicon molecular sieve TS-1 is not the most provided that enough urging
Change activity, be in the state of inactivation.Here inactive titanium silicon molecule sieve catalyst can derive from industry inactivation
Agent or the decaying catalyst after carrying out oxidation reaction in the lab.
The present invention provide renovation process may be used for process alkene epoxidation, arene hydroxylation, ketone oxamidinating,
The oxidation of alcohol or oxidation of alkanes reaction, such as phenol hydroxylation, cyclohexanone oxamidinating, propylene ring oxidation reaction
Middle occur that the titanium silicon of deactivation phenomenom (as conversion ratio or selectivity decrease beyond 2%) divides after a period of time operates
Sub-sieve catalyst.In the case of particularly in existing conventional device, technical finesse means effect is undesirable, such as warp
Cross the Regeneration Treatment such as solvent washing when catalyst activity but can not be made to return to acceptable level, use this
The method of bright offer can obtain satisfied activation recovering effect.
In the renovation process that the present invention provides, the HTS of described inactivation can be the titanium of MFI structure
Si molecular sieves (such as TS-1), the HTS (such as TS-2) of MEL structure, the titanium silicon molecule of BEA structure
Sieve (such as Ti-Beta), the HTS (such as Ti-MCM-22) of MWW structure, the titanium of two dimension hexagonal structure
Si molecular sieves (such as Ti-MCM-41, Ti-SBA-15), the HTS (such as Ti-MOR) of MOR structure,
The HTS (such as Ti-TUN) of TUN structure and the HTS (such as Ti-ZSM-48) of other structures
In at least one.Under preferable case, described deactivated titanium silicon molecular sieve be MFI structure HTS,
One or more in the HTS of MEL structure and the HTS of BEA structure, more preferably MFI
The HTS of structure, it is highly preferred that the MFI knot that described deactivated titanium silicon molecular sieve is hollow-core construction crystal grain
Structure HTS, the radical length of the chamber portion of this hollow-core construction is 5～300nm.
In the renovation process that the present invention provides, described by the HTS of inactivation with selected from dimethyl sulfoxide,
In sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide at least one
Plant compound contact.Described contact, is to carry out under the boiling point less than described compound, along with not
Otherwise varied with compound, this is well known to those skilled in the art.Under normal pressure, dimethyl is sub-
The boiling point of sulfone, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
It is respectively 189 DEG C, 285 DEG C, 202 DEG C, 153 DEG C and 96 DEG C.Angularly consider from reducing energy consumption, its
Further preferred contact conditions is Contact Temperature room temperature～96 DEG C, pressure 0.001～1.0MPa.Above-mentioned chemical combination
Thing the most strictly limits with the ratio of deactivated titanium silicon molecular sieve, as long as the present invention can be realized.From operation
Convenience and conservation angularly consider, above-claimed cpd is preferably with the mass ratio of deactivated titanium silicon molecular sieve
0.5～100:1, more preferably 2～50:1.
In the renovation process that the present invention provides, described alkaline solution can be organic basic solution, it is also possible to
Inorganic caustic solutions, wherein described inorganic alkali solution be selected from by ammonia, alkali metal and or alkaline-earth metal,
Or the solution that basic salt is formed, the example of inorganic base can be but be not limited to ammonia, sodium hydroxide, hydrogen-oxygen
Change potassium, calcium hydroxide, Lithium hydrate, sodium carbonate, potassium carbonate etc., preferably ammonia；Described organic base
Example can be but be not limited to TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, four
Butyl ammonium hydroxide, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanol
One or more in amine, diethanolamine, triethanolamine, multiple situation such as, tetraethyl ammonium hydroxide
With the mixture of the mixture of n-butylamine, tetraethyl ammonium hydroxide and n-butylamine, ethylenediamine and tetrapropyl hydrogen-oxygen
Change the mixture of ammonium, di-n-propylamine and the mixture of TPAOH, tetraethyl ammonium hydroxide and 4 third
The mixture of the mixture of base ammonium hydroxide, hexamethylene diamine and TPAOH may be incorporated for the present invention,
And the ratio for above-mentioned mixing does not has particular/special requirement yet, as long as the present invention can be realized.Described alkali
Property solution more preferably organic basic solution.Described its pH value of alkaline solution preferably 8～14.
In the renovation process that the present invention provides, the described product after contact and alkaline solution mixed processing, its
Condition is to be 20～100 DEG C and pressure is under 0.0～3.0MPa in temperature, utilize alkaline solution rinse 0.5～
72h。
The present invention provide renovation process in, through with alkaline solution mixed processing after, HTS product root
Further activation process can also be carried out according to needs, as between 100～300 DEG C be dried and purging 0.1～
10h, and all carry out in nitrogen or air atmosphere.
The present invention provide renovation process in, inventor it has been unexpectedly discovered that, by inactivation HTS with
Selected from dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and N, N-dimethyl
During at least one compound contact in acetamide, being simultaneously introduced the mass ratio with above-mentioned substance is
0.0001～0.1:1 ammonia time, the recovery time can be saved, improve further the effect of regeneration, and make
The described the most separated repeated multiple times use capable of circulation of compound.Therefore, the present invention's is preferred
Embodiment be by inactivation HTS with selected from dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone,
DMF contacts with at least one compound in N,N-dimethylacetamide, be simultaneously introduced with
The mass ratio of above-claimed cpd is (0.0001～0.1): the ammonia of 1, then by the product after contact with a kind of
Alkaline solution mixed processing also activates further.Wherein, described activation is to be dried at 100～300 DEG C and blow
Sweep 0.1～10h, and all carry out in nitrogen or air atmosphere.The ammonia of described introducing can be with the form of liquefied ammonia
Introduce, it is possible to introduce as an aqueous solution, it is also possible to the form of gas introduces.Ammonia as aqueous solution form
The concentration of (that is, ammonia) is not particularly limited, and can be conventional selection, such as 1～36wt%.
Below by embodiment, the invention will be further described, but and is not so limited present disclosure.
In comparative example and embodiment, used reagent is commercially available chemically pure reagent.
In comparative example and embodiment, titanium-silicon molecular sieve TS-1 used be according to document " Zeolites, 1992,
Vol.12:943～950 " described in method prepare, its titanium oxide content is 2.5wt%.Used
Hollow titanium si molecular sieves HTS be according to CN1132699C disclosed in method prepare, through analyze, this titanium silicon
Molecular sieve is MFI structure, the adsorption isotherm of the nitrogen absorption under low temperature of this HTS and desorption isotherm it
Between there is hysteresis loop, crystal grain be the radical length of hollow crystal grain and chamber portion be 15～180nm；This titanium silicon divides
Son sieve sample at 25 DEG C, P/P0=0.10, adsorption time is that the benzene adsorbance recorded under conditions of 1h is
78mg/g, its titanium oxide content is 2.5wt%.
In comparative example and embodiment, relative crystallinity is with gained sample and standard specimen each X-ray diffraction
(XRD) the peak height sum of the 2 θ angles five diffraction maximums (characteristic diffraction peak) between 22.5～25.0 °
Ratio represent, standard specimen (its degree of crystallinity is set to 100%) herein for according to " Zeolites, 1992,
Vol.12:943～950 " the TS-1 molecular sieve sample that i.e. comparative example 1 obtains prepared.
Comparative example 1
This comparative example is the method system described in " Zeolites, 1992, Vol.12:943～950 "
The process of standby TS-1 sieve sample.
22.5g tetraethyl orthosilicate is mixed with 7.0g TPAOH, and adds 59.8g distilled water,
At normal pressure and 60 DEG C, hydrolyze 1.0h after mix homogeneously, be slowly added into the most with vigorous stirring by 1.1g
The solution that butyl titanate and 5.0g anhydrous isopropyl alcohol are formed, stirs 3h at 75 DEG C by gained mixture,
Obtain clear colloid.This colloid is put into rustless steel sealed reactor, and at a temperature of 170 DEG C, constant temperature is put
Put 3d, obtain the mixture of crystallization product；This mixture is filtered, washes with water, and is dried in 110 DEG C
1h, then at 550 DEG C of roasting temperature 3h, obtains TS-1 molecular sieve.
Comparative example 2
This comparative example explanation HTS of inactivation in phenol hydroxylation reacts uses the mistake of roasting regeneration
Journey.
Comparative example 1 preparation TS-1 sample phenol hydroxylation react in, phenol and hydrogen peroxide mol ratio 3:1
With acetone as solvent, after reacting 4h at 80 DEG C, catalyst is separated from reaction system, be dried, be used further to
Next round is reacted, and after so circulating 5 times, activity is reduced to original about 50%, isolates catalyst, is dried
Postscript is SH-1.Catalyst is separated, is dried, is then passed through 550 DEG C of roasting 3h, obtains roasting regeneration sample
Product, are designated as BS-1.
Comparative example 3
This comparative example explanation HTS of inactivation in cyclohexanone oxamidinating reacts uses the mistake of roasting regeneration
Journey.
Take TS-1 molecular sieve TS-1 to be placed in 100mL band continuous feed and membrane separation device slurry bed reactor,
Add mixture (water and the peroxide of the hydrogen peroxide of water and 30wt% with the speed of 5.7mL/h under stirring
The volume ratio changing hydrogen is 10:9), add Ketohexamethylene and the mixture (ring of the tert-butyl alcohol with the speed of 10.5mL/h
The volume ratio of hexanone and the tert-butyl alcohol is 1:2.5), add 25wt% ammonia with the speed of 5.7mL/h, above-mentioned three
Stock material stream is for being simultaneously introduced, and simultaneously with corresponding speed continuous discharge, reaction temperature maintains 80 DEG C, instead
Every 12h, product sampling chromatograph is analyzed after should stablizing.Through after a while, Ketohexamethylene conversion ratio
After being dropped to 50% by initial 95%, isolate catalyst, be designated as SH-2 after drying.SH-2 sample roasts
Burning regeneration regenerate, will sample SH-2 at 570 DEG C in air atmosphere roasting 4h, obtain roasting regeneration
Sample, sample is designated as BS-2.
Comparative example 4
The HTS that the explanation of this comparative example inactivates in cyclohexanone oxamidinating reacts is according to CN1461671A side
The regenerative process of method.
The method that SH-2 describes according to CN1461671A embodiment 1 is processed molecular sieve, and sample is designated as BS-3.
Concrete processing procedure is as follows: by 9 grams of SH-2 samples and 180 gram of 5% dust technology mixing, with 85 DEG C of stirrings 2
Hour, filtering, solid deionized water rinses repeatedly, and 120 DEG C are dried, and 560 DEG C of roastings 6 hours,
Obtain regeneration Ti-Si catalyst BS-3.
Comparative example 5
The process that the HTS of this comparative example explanation propylene ring oxidation reaction inactivation regenerates with method of roasting.
Take hollow titanium si molecular sieves HTS and be placed in 100mL band continuous feed and membrane separation device slurry bed reactor
In, under stirring, the mixture (first of the hydrogen peroxide of methanol and 30wt% is added with the speed of 50mL/h
Alcohol is 10:1 with the mass ratio of hydrogen peroxide), add propylene with the speed of 10mL/h, above-mentioned material stream is same
Time add, and with corresponding speed continuous discharge, reaction temperature maintains 40 DEG C, and pressure maintains 2MPa,
Every 12h, product sampling chromatograph is analyzed after stable reaction.Through after a while, hydrogen peroxide turns
After rate is dropped to 80% by initial 95%, isolate catalyst, be designated as SH-3 after drying.SH-3 sample
Regenerate by roasting regeneration mode, will sample SH-3 at 570 DEG C in air atmosphere roasting 4h, obtain roasting
Regeneration sample, sample is designated as BS-4.
Comparative example 6
The HTS that the explanation of this comparative example inactivates in propylene ring oxidation reaction is according to CN1461671A method
Regenerative process.
The method that SH-3 describes according to CN1461671A embodiment 1 is processed molecular sieve, and sample is designated as BS-5.
Concrete processing procedure is as follows: by 9 grams of SH-3 samples and 180 gram of 5% dust technology mixing, with 85 DEG C of stirrings 2
Hour, filtering, solid deionized water rinses repeatedly, and 120 DEG C are dried, and 560 DEG C of roastings 6 hours,
Obtain regeneration Ti-Si catalyst BS-5.
Embodiment 1
Under the conditions of normal pressure 90 DEG C, the deactivated titanium silicon molecular sieve (SH-2) of dimethyl sulfoxide with comparative example 4 is mixed
Splice grafting touches 5.5h, and wherein deactivated titanium silicon molecular sieve is 1:10 with the weight ratio of dimethyl sulfoxide, often after taking-up
Under the conditions of pressing 90 DEG C, the ammonia spirit utilizing pH to be 10 rinses 0.5h, the molecular sieve-4 A after being processed.
Embodiment 2
At normal pressure 80 DEG C, dimethyl sulfoxide is mixed with the deactivated titanium silicon molecular sieve (SH-3) of comparative example 5 and connects
Touching 7.5h, wherein deactivated titanium silicon molecular sieve is 1:5 with the weight ratio of dimethyl sulfoxide.Then by molecular sieve often
Under the conditions of pressing 80 DEG C, the ammonia spirit utilizing pH to be 10 rinses 0.1h, the molecular sieve B after being processed.
Embodiment 3
Under the conditions of normal pressure 90 DEG C, the deactivated titanium silicon molecular sieve (SH-2) of dimethyl sulfoxide with comparative example 4 is mixed
Splice grafting touches 5.5h, and wherein deactivated titanium silicon molecular sieve is 1:10 with the weight ratio of dimethyl sulfoxide, often after taking-up
Under the conditions of pressing 90 DEG C, the ammonia spirit utilizing pH to be 10 rinses 0.5h, then at air after taking-up molecular sieve
120 DEG C of dry 3h in atmosphere, the molecular sieve C after being processed.
Embodiment 4
Under the conditions of normal pressure 80 DEG C, the deactivated titanium silicon molecular sieve (SH-3) of dimethyl sulfoxide with comparative example 5 is mixed
Splice grafting touches 7.5h, and wherein deactivated titanium silicon molecular sieve is 1:5 with the weight ratio of dimethyl sulfoxide.Then by molecular sieve
Under the conditions of normal pressure 80 DEG C, the ammonia spirit utilizing pH to be 10 rinses 0.1h, then by molecular sieve at air
150 DEG C of dry 5h in atmosphere, the molecular sieve D after being processed.
Embodiment 5
Under the conditions of normal pressure 90 DEG C, the deactivated titanium silicon molecular sieve (SH-2) of dimethyl sulfoxide with comparative example 4 is mixed
Splice grafting touches, and wherein deactivated titanium silicon molecular sieve is 1:10 with the weight ratio of dimethyl sulfoxide, is simultaneously introduced and dimethyl
The mass ratio of sulfoxide is the liquefied ammonia of 0.01:1, takes out molecular sieve and after contact 2.5h under the conditions of normal pressure 90 DEG C,
The ammonia spirit utilizing pH to be 10 rinses 0.5h, then by molecular sieve 120 DEG C of dry 3h in air atmosphere,
Molecular sieve E after being processed.
Embodiment 6
Under the conditions of normal pressure 80 DEG C, the deactivated titanium silicon molecular sieve (SH-3) of dimethyl sulfoxide with comparative example 5 is mixed
Splice grafting touches, and wherein deactivated titanium silicon molecular sieve is 1:5 with the weight ratio of dimethyl sulfoxide, is simultaneously introduced and dimethyl
The mass ratio of sulfoxide is the liquefied ammonia of 0.01:1, takes out under the conditions of normal pressure 80 DEG C, utilize after contact 1.5h
PH is the ammonia spirit flushing 0.1h of 10, then by molecular sieve 120 DEG C of dry 3h in air atmosphere,
Molecular sieve F after process.
Comparative example 7
Process deactivated titanium silicon molecular sieve according to the method for embodiment 3, save the step that wherein ammonia rinses.I.e.
Under the conditions of normal pressure 90 DEG C, dimethyl sulfoxide is mixed with the deactivated titanium silicon molecular sieve (SH-2) of comparative example 4 and connects
Touching 5.5h, wherein deactivated titanium silicon molecular sieve is 1:10 with the weight ratio of dimethyl sulfoxide, is then existed by molecular sieve
120 DEG C of dry 3h in air atmosphere, the molecular sieve DB-1 after being processed.
Comparative example 8
Process deactivated titanium silicon molecular sieve according to the method for embodiment 4, save the step that wherein ammonia rinses.I.e.
Under the conditions of normal pressure 80 DEG C, dimethyl sulfoxide is mixed with the deactivated titanium silicon molecular sieve (SH-3) of comparative example 5 and connects
Touching 7.5h, wherein deactivated titanium silicon molecular sieve is 1:5 with the weight ratio of dimethyl sulfoxide.Then by molecular sieve at sky
150 DEG C of dry 5h in gas atmosphere, the molecular sieve DB-2 after being processed.
Comparative example 9
Process deactivated titanium silicon molecular sieve according to the method for embodiment 5, save the step that wherein ammonia rinses.I.e.
Under the conditions of normal pressure 90 DEG C, dimethyl sulfoxide is mixed with the deactivated titanium silicon molecular sieve (SH-3) of comparative example 5 and connects
Touching, wherein deactivated titanium silicon molecular sieve is 1:10 with the weight ratio of dimethyl sulfoxide, is simultaneously introduced and dimethyl sulfoxide
The liquefied ammonia that mass ratio is 0.01:1, take out and by molecular sieve in air atmosphere 120 DEG C after contact 2.5h
It is dried 3h, the molecular sieve DB-3 after being processed.
Comparative example 10
Process deactivated titanium silicon molecular sieve according to the method for embodiment 6, save the step that wherein ammonia rinses.I.e.
Under the conditions of normal pressure 80 DEG C, dimethyl sulfoxide is mixed with the deactivated titanium silicon molecular sieve (SH-3) of comparative example 5 and connects
Touching, wherein deactivated titanium silicon molecular sieve is 1:5 with the weight ratio of dimethyl sulfoxide, is simultaneously introduced and dimethyl sulfoxide
The liquefied ammonia that mass ratio is 0.01:1, take out and by molecular sieve in air atmosphere 150 DEG C after contact 1.5h
It is dried 2h, the molecular sieve DB-4 after being processed.
Embodiment 7
Under the conditions of 50 DEG C and 0.05MPa, by the deactivated titanium silicon molecular sieve (SH-3) of sulfolane Yu comparative example 5
Mixing contact 5h, wherein deactivated titanium silicon molecular sieve is 1:2 with the weight ratio of sulfolane, normal pressure 70 DEG C after taking-up
Under the conditions of, the n-butylamine solution utilizing pH to be 12 rinses 0.5h, then at air atmosphere after taking-up molecular sieve
In 120 DEG C of dry 3h, the molecular sieve G after being processed.
Embodiment 8
Under the conditions of normal pressure 60 DEG C, by the deactivated titanium silicon molecular sieve of N-Methyl pyrrolidone Yu comparative example 5
(SH-3) mixing contact 15h, wherein deactivated titanium silicon molecular sieve is 1 with the weight ratio of N-Methyl pyrrolidone:
25.Then, by molecular sieve under the conditions of normal pressure 80 DEG C, the diethanolamine solution utilizing pH to be 11 rinses 6h,
Then by molecular sieve 150 DEG C of dry 5h in air atmosphere, the molecular sieve H after being processed.
Embodiment 9
Under the conditions of normal pressure 90 DEG C, by the deactivated titanium silicon molecular sieve of DMF Yu comparative example 4
(SH-2) mixing contact, wherein deactivated titanium silicon molecular sieve is 1 with the weight ratio of DMF:
15, it is simultaneously introduced the liquefied ammonia that the mass ratio with dimethyl sulfoxide is 0.005:1, takes out after contact 2.5h and divide
Son sieves and at normal pressure 90 DEG C, the hexamethylene diamine utilizing pH to be 13 and the mixed solution punching of TPAOH
Wash 0.5h, then by molecular sieve 200 DEG C of dry 3h in air atmosphere, the molecular sieve I after being processed.
Embodiment 10
Under the conditions of normal pressure 80 DEG C, by the deactivated titanium silicon molecular sieve of N,N-dimethylacetamide Yu comparative example 5
(SH-3) mixing contact, wherein deactivated titanium silicon molecular sieve is 1 with the weight ratio of N,N-dimethylacetamide:
50, it is simultaneously introduced the liquefied ammonia that the mass ratio with dimethyl sulfoxide is 0.05:1, takes out often after contact 1.5h
Under the conditions of pressing 80 DEG C, the TPAOH solution utilizing pH to be 12 rinses 0.1h, then by molecular sieve
120 DEG C of dry 3h in air atmosphere, the molecular sieve J after being processed.
Embodiment 11
Deactivated titanium silicon molecular sieve, except for the difference that deactivated titanium silicon molecular sieve and ring is processed according to the method for embodiment 7
The weight ratio of fourth sulfone is 1:1, the molecular sieve K after being processed.
Embodiment 12
Deactivated titanium silicon molecular sieve, except for the difference that deactivated titanium silicon molecular sieve and ring is processed according to the method for embodiment 7
The weight ratio of fourth sulfone is 1:55, the molecular sieve L after being processed.
Test case
This test case illustrate molecular sieve-4 A that the inventive method regenerates～L and the molecular sieve TS-1 of comparative example method,
HTS, SH-1～SH-3, BS-1～BS-5, DB-1～DB-4 are used for the catalytic oxidation of phenol hydroxylation
Effect.
According to molecular sieve: phenol: the weight ratio of acetone=1:20:16 is at the there-necked flask of a band condensing tube
Middle mix homogeneously, is warming up to 80 DEG C, then according to phenol under stirring: hydrogen peroxide=1:0.39's
It is the hydrogen peroxide of 30wt% that weight ratio adds concentration, reacts 4h at this temperature, and products therefrom is at 6890N
Measure phenol conversion on type gas chromatograph, the results are shown in Table 1.
As can be seen from Table 1, after the regeneration that obtains of renovation process that the present invention provides HTS with
The roasting of prior art or pickling add the regeneration HTS that the method for roasting obtains and compare, catalytic performance
More superior, and relative crystallinity and micropore specific area the most substantially completely recover.Particularly introducing two
Methyl sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
In at least one compound while, add a small amount of ammonia, can further improve the effect of regeneration.
Table 1
| Sample | Phenol conversion, % | Relative crystallinity, % | Micropore specific area, m2/g |
| TS-1 | 25.2 | 100 | 375 |
| SH-1 | 12.8 | 82 | 258 |
| BS-1 | 22.6 | 96 | 347 |
| SH-2 | 11.6 | 89 | 296 |
| BS-2 | 17.9 | 93 | 325 |
| BS-3 | 21.7 | 94 | 338 |
| HTS | 26.1 | 101 | 369 |
| SH-3 | 11.6 | 89 | 296 |
| BS-4 | 20.3 | 95 | 331 |
| BS-5 | 18.1 | 91 | 342 |
| A | 21.3 | 96 | 361 |
| B | 22.6 | 98 | 353 |
| C | 23.1 | 99 | 368 |
| D | 25.0 | 100 | 361 |
| E | 24.2 | 99 | 370 |
| F | 25.8 | 101 | 364 |
| DB-1 | 21.4 | 96 | 363 |
| DB-2 | 23.2 | 99 | 360 |
| DB-3 | 22.8 | 97 | 366 |
| DB-4 | 25.1 | 100 | 357 |
| G | 23.5 | 98 | 351 |
| H | 22.3 | 99 | 345 |
| I | 24.5 | 100 | 367 |
| J | 23.9 | 99 | 354 |
| K | 20.6 | 93 | 322 |
| L | 21.1 | 99 | 353 |
Claims (8)
1. the renovation process of a HTS, it is characterised in that include by the HTS of inactivation be selected from
Dimethyl sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and N, N-diformazan
At least one compound contact in yl acetamide, then by the product after contact and a kind of alkaline solution
The step of mixed processing 0.5～72h at temperature 20～96 DEG C and pressure 0.0～3.0MPa, and
Further activation process；In described contact, described compound and described deactivated titanium silicon molecule
The mass ratio of sieve is 0.5～100:1, and Contact Temperature is less than the boiling point of described compound；Described work
Change process is to be dried and purge 0.1～10h at 100～300 DEG C and all enter in nitrogen or air atmosphere
OK.
2., according to the process of claim 1 wherein, the HTS of described inactivation is the titanium of MFI structure
Si molecular sieves, the HTS of MEL structure, the HTS of BEA structure, the titanium of MWW structure
Si molecular sieves, the two dimension HTS of hexagonal structure, the HTS of MOR structure, TUN structure
HTS and Ti-ZSM-48 at least one.
3., according to the process of claim 1 wherein, the HTS of described inactivation is the titanium of MFI structure
One or many in the HTS of si molecular sieves, the HTS of MEL structure and BEA structure
Kind.
4., according to the process of claim 1 wherein, the HTS of described inactivation is hollow-core construction crystal grain
MFI structure HTS, the radical length of the chamber portion of this hollow-core construction is 5～300nm.
5. the HTS of according to the method for one of Claims 1 to 4, wherein, described inactivation is from alkene
Epoxidation, arene hydroxylation, ketone oxamidinating, the oxidation of alcohol or oxidation of alkanes reaction.
6., according to the process of claim 1 wherein, described alkaline solution is selected from ammonia, sodium hydroxide, hydrogen
Potassium oxide, calcium hydroxide, Lithium hydrate, sodium carbonate, potassium carbonate, TPAOH, tetrem
Base ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, n-propylamine, n-butylamine,
In di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanolamine, triethanolamine solution one
Plant or multiple.
7. according to the process of claim 1 wherein described alkaline solution, pH value 8～14.
8. according to the process of claim 1 wherein, described contact, be simultaneously introduced ammonia, ammonia with selected from diformazan
Base sulfoxide, sulfolane, N-Methyl pyrrolidone, N,N-dimethylformamide and N, N-dimethyl second
The mass ratio of at least one material in amide is (0.0001～0.1): 1.
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| CN102463123A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Activation method of catalyst |
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| CN102463123A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Activation method of catalyst |
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