CN102513152B - Regeneration method of titanium silicate molecular sieve catalyst - Google Patents
Regeneration method of titanium silicate molecular sieve catalyst Download PDFInfo
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Abstract
The invention relates to a regeneration method of a titanium silicate molecular sieve catalyst, comprising the following steps of: compounding and regenerating an inactivated catalyst by the following steps of: A: roasting the inactivated catalyst for 2-10 hours; and B: carrying out secondary crystallization on the roasted molecular sieve catalyst. The secondary crystallization comprises the following steps of: carrying out hydrothermal crystallization in a secondary crystallization solution with the pH value of 8-13 at a temperature in a range of 130-190 DEG C and at sealed inner pressure for 12-120 hours, wherein the secondary crystallization solution is an aqueous solution containing one or more substances of ammonium salt, aqueous ammonia and organic amine; and then washing and drying to prepare a titanium silicate molecular sieve, wherein preferably, a titanium source is added into the secondary crystallization solution obtained in the step B. The preparation method provided by the invention has the advantages of simplicity in operation and easiness in controlling the process; and the activity of the regenerated titanium silicate molecular sieve can reach and even exceed the level of a fresh titanium silicate molecular sieve catalyst.
Description
Technical field
The present invention relates to the renovation process of the catalyst of inactivation, be specifically related to the renovation process of HTS.
Background technology
HTS has absorption and the Studies On The Shape-selective Catalysis of molecular sieve, have again the catalysed oxidn of titanium avtive spot concurrently, thereby it is widely used in the selective oxidation reaction that catalysis hydrogen peroxide carries out.As titanium-silicon molecular sieve TS-1 is mainly used in the following oxidation reaction of catalysis at present: alkene epoxidation, alcohol oxidation, partial oxidation of alkanes, phenol hydroxylation, aromatic hydrocarbon epoxidation, ammoxidation of cyclohexanone etc.The above-mentioned oxidation reaction of Peroxide Catalyzed by Titanium Silicalite-1 has desirable catalytic activity and selectivity of product mostly, thereby but catalyst is easy to inactivation has limited its large-scale commercial Application.
In prior art, the regeneration of inactive titanium silicon molecule sieve catalyst is generally taked to two kinds of modes, first roasting at 550 DEG C; Another kind method is under heating up, to wash to recover catalyst activity with solvent.As described a kind of renovation process of titanium-silicon molecular sieve catalyst in Chinese patent application CN101602011A, wherein the HTS Ti-MWW of inactivation comes from the epoxidation reaction of alkene and the Ammoximation reaction of ketone, the method is first through acid compound solution-treated by the HTS of inactivation, again through alkaline compound solution hydrothermal treatment consists under the self-generated pressure of 120-200 DEG C, then after filtration, washing, dry, roasting, obtain the HTS of regeneration.Wherein said acid compound is one or more in hydrochloric acid, sulfuric acid and nitric acid; Described alkali compounds is piperidines, hexamethylene imine or its mixture.
In patent US6066750A, a kind of Efficient Ring oxidizing process is described, prepare in propane and use TS-1 as catalyst at epoxidation of propylene, use at the temperature of a kind of solvent more than 150 DEG C drip washing TS-1 to make its regeneration, the mixed solution of the aliphatic alcohol and water that this solvent is is 10-500ppm containing ammonium or alkali metal cation amount.If ammonium phosphate, ammonium sulfate, carboxylic acid ammonium, ammonium carbonate, ammonium nitrate, ammoniacal liquor, sodium chloride, potassium nitrate, sodium sulphate, potash, sodium acid carbonate, sodium acetate, sodium phosphate or the NaOH etc. that dissolve 10-500ppm in isopropyl alcohol and water (6.3: 1) are as regenerated solvent.
No matter be roasting regeneration, or solvent heat regenerated from washing HTS, its regeneration effect to deactivated molecular sieve is limited, and the high energy of catalyst after regeneration returns to the activity level of fresh catalyst.The multiple bibliographic data bases discoveries in retrieval China and foreign countries, in prior art, rarely the deactivation cause to HTS is made research, also less than the report being combined with of regenerating about roasting regeneration and solvent wash.
In prior art, use secondary crystallization method to carry out modification to improve catalyst activity, as having report in patent application CN101786638A to fresh HTS.But never this type of method of modifying is made the report of the reason that titanium molecular sieve catalysis activity significantly promotes.
The inventor draws research conclusion through a large amount of experiment and signs, be that the reason that secondary crystallization modification HTS significantly promotes its activity is, under the specified conditions of secondary crystallization, extra-framework titanium in HTS after crystallization reenters skeleton first, has increased titanium avtive spot (this content will be explained below).Secondary crystallization scheme can make up the titanium avtive spot running off in deactivated titanium silicon molecular sieve, and the active sites of the HTS that even can make to regenerate is counted higher than fresh HTS.But the effective prerequisite of secondary crystallization regeneration scheme is that deactivated titanium silicon molecular sieve inner duct is unimpeded, also before secondary crystallization regeneration, need deactivated titanium silicon molecular sieve roasting with dredging duct.
In the present invention, consider above-mentioned two kinds of inactivations of HTS simultaneously, make titanium-silicon molecular sieve catalyst activity after regenerating approach the activity of fresh catalyst, even can be higher than the activity of fresh catalyst.
In a preferred embodiment of the present invention, the described composite regenerated step C also comprising after step B, by the HTS roasting 0.5-10 hour after secondary crystallization.The roasting of this step can be removed plane of crystal stress, is conducive to framework of molecular sieve stable.
In step C of the present invention, described sintering temperature conventional sintering temperature can be those skilled in the art's roasting HTS time, for example conventional is 450～650 DEG C, preferably 550 DEG C.
In another preferred embodiment of the present invention, in described step B, in secondary crystallization solution, also comprise titanium sulfate and/or titanium trichloride as titanium source.Increase because the meaning of secondary crystallization is to make titanium avtive spot on molecular sieve, in secondary crystallization solution, add a certain amount of titanium source, will be conducive to form more titanium avtive spots.In fact, in preparation fresh titanium silicalite molecular sieve catalyst process, if before crystallization first prepare sol-process in add too much titanium source, will cause it to become gel, thus to crystallization is totally unfavorable first.And experiment showed, that it is feasible in the solution of secondary crystallization, mending titanium, supplementary titanium source can be titanium sulfate as above or titanium trichloride etc.
Above-mentioned two kinds of titanium sources are compared, more preferably titanium sulfate.In fact, no matter be the titanium trichloride of trivalent or the titanium sulfate of tetravalence, can in secondary crystallization, enter framework of molecular sieve, and the catalytic activity of two kinds of molecular sieves that finally regeneration obtains is suitable.But because titanium sulfate is neutral compound, and titanium trichloride (the general hydrochloric acid solution using containing titanium trichloride 15%) is highly acid; Secondary crystallization solution finally needs an alkaline environment, thereby uses titanium sulfate will make utilization rate of equipment and installations higher.Equally, compare from toxicity and cost of material aspect, also preferably sulfuric acid titanium is as titanium source.
Those skilled in the art will appreciate that in steps A, the catalyst of described inactivation can be through repeatedly regeneration and the repeatedly titanium-silicon molecular sieve catalyst of inactivation.That is to say, this decaying catalyst can be before this through the decaying catalyst of roasting regeneration repeatedly or additive method regeneration.
In another preferred embodiment of the present invention, in step B, secondary crystallization solution is ammoniacal liquor, and its weight concentration is 0.1-30%; Or secondary crystallization solution is the mixed liquor in ammoniacal liquor and titanium source, and wherein the weight concentration of ammoniacal liquor is 0.1-30%.Preferably wherein ammonia concn is 0.2-10%, more preferably 1-5% again.
In another preferred embodiment of the present invention, in step B, pH value is 10-12, and hydrothermal temperature is 160～180 DEG C, more preferably 170 DEG C.
Do above-mentioned preferred reason and come from the optimal conditions of choosing secondary crystallization modification TS-1 molecular sieve, in detail can be with reference to master thesis " secondary crystallization method modification TS-1 molecular sieve and catalysis chloro propylene epoxidation performance thereof " (Ou Ying, University Of Xiangtan, 2009).In this paper, investigate the various effects of ammonium salt solution as secondary crystallization solution that contain, result is to use the catalyst activity of ammoniacal liquor, carbonic hydroammonium, ammonium sulfate, ammonium acetate and ammonium nitrate secondary crystallization gained to reduce successively.Then investigated the impact of the basicity of secondary crystallization solution, the too low effect that cannot produce secondary crystallization of basicity; And basicity too high (as pH=13) is the little crystal grain corrosion causing in TS-1 molecular sieve, catalyst activity is subject to certain destruction.This paper also points out, the anion optimum in secondary crystallization solution is OH
-, and the anion such as carbanion, sulfate ion, acetate ion, nitrate ion are all unfavorable to secondary crystallization to a certain extent.Cation in secondary crystallization solution can be NH
4 +if, but TPA
+etc. organic containing ammonium ion modified effect better (as use TPAOH), consider cost of material factor, weak aqua ammonia as secondary crystallization solution without the advantage being suspected to have clearly.In addition, the cation in secondary crystallization solution does not preferably comprise Na
+, K
+deng alkali metal ion, as add a small amount of NaOH as secondary crystallization solution, all will cause the very big destruction of framework of molecular sieve, even molecular sieve all changes the gel that there is no catalytic activity into.
Summary of the invention
The invention provides a kind of renovation process of titanium-silicon molecular sieve catalyst, comprise the catalyst of inactivation composite regenerated through following steps: steps A, by the catalyst roasting 2-10 hour of inactivation; Step B, molecular sieve catalyst after roasting is carried out to secondary crystallization, in the secondary crystallization solution that it is 8-13 that described secondary crystallization refers in pH value, 130-190 DEG C and sealing self-generated pressure under hydrothermal crystallizing 12-120 hour, wherein secondary crystallization solution is the aqueous solution that comprises one or more materials in ammonium salt, ammoniacal liquor and organic amine; Then through washing and the dry HTS for preparing regeneration.
In steps A of the present invention, described sintering temperature conventional sintering temperature can be those skilled in the art's roasting HTS time, for example conventional is 450～650 DEG C, preferably 550 DEG C.
The regeneration of catalyst and the inactivation of catalyst are closely connected.The inactivation of molecular sieve catalyst is point two classes generally, and a class is temporary inactivation, as accessory substance in molecular sieve causes the inactivation of duct due to stopping up; Another kind of is permanent inactivation, as the loss of active site, and mechanical wear, structure is caved in, and Impurity deposition is poisoning etc.The inactivation occurring on HTS mainly contains two kinds, and one is that oxidized byproduct stops up molecular sieve pore passage, and another kind is the loss of titanium avtive spot; Inventor's process studies and experiment draws, the preferred solution that on HTS, accessory substance stops up is roasting, and the loss of titanium avtive spot suitable use secondary crystallization is repaired.
The present invention uses existing roasting regeneration technology, and secondary crystallization method (the former modification for fresh catalyst) is applied to regenerating molecular sieve field, in conjunction with these two kinds of method regeneration HTSs, and has obtained unexpected technique effect.By controlling composite regenerated condition, the activity of the HTS after regeneration can be higher than fresh catalyst.
Detailed description of the invention
Below be only the preferred embodiment of the present invention, protection scope of the present invention is not limited to this, and any those skilled in the art is in technical scope disclosed by the invention, within can being easy to the change carried out or changing and be encompassed in protection scope of the present invention.
In following examples, all taking titanium-silicon molecular sieve TS-1 as example, but those skilled in the art will appreciate that this catalyst recovery process is equally applicable to other HTSs as TS-2, Ti-MWW and Ti-MCM-41 etc.
The preparation process of the silicalite TS-1 of fresh titanium described in the embodiment of the present invention is: colloid preparation → crystallization → roasting → secondary crystallization → roasting first obtains fresh titanium silicalite TS-1 after above-mentioned five steps; That is to say, described fresh titanium silicalite TS-1 refers to the TS-1 after secondary crystallization modification herein.Its concrete synthesis step is: taking Ludox as silicon source, TiCl
3the aqueous solution or Ti (SO
4)
2crystal is that titanium source, TPAOH (TPAOH) are template, ammoniacal liquor adjusting basicity; Silicon source, template, titanium source and deionized water are added successively according to a certain percentage, after fully stirring, with ammoniacal liquor regulate basicity to pH be 11-13, add appropriate TS-1 molecular sieve to make crystal seed and make glue, glue proportioning is as follows: n (SiO
2): n (TiO
2): n (TPAOH): m (H
2o): m (NH
3.H
2o)=1: 0.013-0.025: 0.025-0.1: 35-45: 20-30.By the glue making in autoclave under 170 DEG C of spontaneous Hydro-thermal pressures crystallization 72h, crystallization product is extremely neutral through deionized water washing, dry 12～14h at 100～120 DEG C, then roasting 6～8h at 550 DEG C, obtains the TS-1 molecular sieve catalyst of crystallization first.Under catalyst after crystallization one or more mixed solutions in ammonium salt, ammoniacal liquor or organic amine, be 8-13 secondary crystallization modification at pH first, modification under the spontaneous Hydro-thermal pressure of 170 DEG C crystallization 24h to 72h; Wash, be dried and 550 DEG C of roasting 6～8h, obtain the TS-1 molecular sieve catalyst of secondary crystallization.
Chloropropene (ALC) epoxidation reaction is as the probe reaction of investigating TS-1 activity of molecular sieve catalysts.The reaction of TS-1 catalysis chloro propylene epoxidation is carried out in the there-necked flask of 250ml-1000ml, is equipped with ice water condensation device and constant current sampling system, magnetic agitation, water-bath temperature control.The disposable there-necked flask that inserts of a certain amount of solvent methanol, chloropropene, hydrogen peroxide and TS-1 raw material, the primary product of reaction is epoxychloropropane ECH, Main By product is chlorine Isopropanediol monomethyl ether.Use iodometric determination H
2o
2residual volume and calculate hydrogen peroxide conversion ratio X
h2O2.With the selective S of Agilent 6890N gas chromatograph analysis epoxychloropropane
eCHwith epoxychloropropane once through yield Y
eCH.
Use the Y of TS-1 molecular sieve (TS-1 of crystallization roasting first) the catalysis chloro propylene epoxidation reaction of not passing through secondary crystallization modification
eCHbe 37.96%; And TS-1 molecular sieve of the same race is in this reaction of catalysis after secondary crystallization modification, gained Y
eCHbe 87.87%.The inventor first explores with experiment and sign the reason that above-mentioned catalyst activity significantly promotes.
First to TS-1 before and after secondary crystallization molecular sieve for IR, Laser particle-size distribution, SEM, XRD and nitrogen adsorb and characterize.Wherein, the SEM sign to TS-1 and Laser particle-size distribution characterize known, and grain size, the pattern of the TS-1 before and after secondary crystallization there is no change; XRD sign to TS-1 is known, and the degree of crystallinity of the TS-1 before and after secondary crystallization does not also change; The nitrogen physical absorption of TS-1 is characterized known, the specific area of the TS-1 before and after secondary crystallization is consistent, nitrogen adsorption/desorption spectrogram is in full accord, illustrate that TS-1 pore passage structure there is no change, and duct quantity does not increase, and the effect of dredging duct is also not obvious; Aforementioned several sign can illustrate that the effect of secondary crystallization modification TS-1 can only be to occur on skeleton, and is to occur in not affect on the titanium of skeleton structure stability avtive spot.And known to the IR sign of TS-1, the I of the TS-1 before and after secondary crystallization
960/ I
800obviously increase, further illustrate increasing of titanium avtive spot.
Secondly, from fresh TS-1 molecular sieve catalyst preparation process, the molecular sieve output in each stage and the difference of catalytic activity are analyzed secondary crystallization and can significantly promote the reason of TS-1 catalytic activity.Bibliographical information, makes elemental analysis to the TS-1 mother liquor after crystallization first with Atomic Emission Spectrometer AES, the in the situation that of TS-1 well-crystallized after crystallization in mother liquor containing titanium elements.Wherein, partial-titanium enters skeleton and forms avtive spot, and we are referred to as skeleton titanium; Another part titanium is attached on skeleton with the form such as load or absorption, and we are referred to as extra-framework titanium.Prepare TS-1 molecular sieve with two batches of raw materials that titaniferous amount is different, all the other raw materials are identical, the wherein titanium source of a collection of use constant, and we are referred to as " general T S-1 "; Another batch used the titanium source of the former 1.3 times of amounts, and we are referred to as " high titanium TS-1 ".After crystallization first, the output of " high titanium TS-1 " molecular sieve is apparently higher than the output of " general T S-1 " molecular sieve.This also illustrates that (the comprising skeleton titanium and extra-framework titanium) that exist on " high titanium TS-1 " molecular sieve total titanium amount will be higher than the former.And two kinds of molecular sieves after crystallization (and roasting) are first carried out to chloro propylene epoxidation reaction and display, the catalytic activity of two kinds of molecular sieves is basic identical, even the catalytic activity of " high titanium TS-1 " molecular sieve than " general T S-1 " slightly a little less than.But after the secondary crystallization modification under the same terms, " high titanium TS-1 " catalyst is obviously high than " general T S-1 " catalyst activity, as the two catalysis chloro propylene epoxidation gained Y
eCHbe respectively 90.80% and 85.24%.
Catalytic reaction activity after crystallization is basically identical first; Illustrate the latter two skeleton Ti contents of crystallization are consistent first, and " high titanium TS-1 " extra-framework titanium content is higher.And the activity of " high titanium TS-1 " molecular sieve after secondary crystallization is obviously higher, illustrate that the extra-framework titanium after crystallization first reenters TS-1 skeleton in secondary crystallization process, also illustrate that secondary crystallization increases the titanium avtive spot of TS-1 molecular sieve.
Above-mentioned experiment and sign all illustrate that the reason that secondary crystallization modification improves TS-1 catalytic activity is: under the secondary crystallization condition of high temperature and middle highly basic degree, extra-framework titanium after a crystallization is dissolved into certain removable state and reenters skeleton, and cause increasing of titanium avtive spot, thereby the activity of catalyst promotes obviously.
The present invention makes based on above-mentioned theory, also, in conjunction with the deactivation cause of HTS and the reason of secondary crystallization modification lifting catalyst activity, gains enlightenment, to solve the regeneration problem of HTS.
Following comparative example and embodiment will be used for explanation, adopt in the present invention roasting regeneration and the secondary crystallization method regeneration of deactivated HTS combining of regenerating, and can reach desirable regeneration effect.
Comparative example 1
Data in table 1 are for illustrating the TS-1 catalyst activity that only passes through roasting regeneration.In table 1, each one way reaction condition is, T=30 DEG C, and t=40min, TS-1 content is 2.37%, n (CH3OH)/n (ALC)=6.5.After each one way reaction just to the roasting regeneration of TS-1 molecular sieve, corresponding seven roastings of seven secondary responses.
Table 1TS-1 is through catalytic perfomance after roasting regeneration repeatedly
As seen from the data in Table 1, through after roasting regeneration repeatedly, TS-1 molecular sieve catalyst is selectively substantially constant to product epoxychloropropane, but catalyst activity successively reduces.This has illustrated that roasting regeneration is the means of effectively regenerating on the one hand, the slowly loss of titanium avtive spot in course of reaction has been described on the other hand, thereby roasting need to just can make the activation recovering of catalyst to higher level in conjunction with other means.
Comparative example 2
Data in this comparative example are for the only TS-1 catalyst activity with solvent wash regeneration is described, comprising using secondary crystallization solution washing regeneration TS-1 molecular sieve.
First experiment has been investigated and has been washed with water, the washing of alcohol wash, acetone, three-in-one reagent (isopyknic methyl alcohol, toluene and acetone) regenerated from washing TS-1 molecular sieve at room temperature and 80 DEG C.Even if use ultrasonic wave to strengthen mass transfer, still can not obviously recover TS-1 activity.For example, again drop into the reaction of catalysis chloro propylene epoxidation by the TS-1 molecular sieve filtration of inactivation, (water) washing with after being dried, it participates in again the Y of catalytic reaction
eCHbe 23.15%; And acetone 80 DEG C of heat washings 2 hours under ultrasonic wave exists for aforementioned TS-1 molecular sieve, after filtration, (water) washing and dry after again drop into the reaction of catalysis chloro propylene epoxidation, its Y
eCHbe 31.33%.Also be that the accessory substance stopping up in TS-1 molecular sieve can not discharge easily.
In addition, under secondary crystallization condition to TS-1 molecular sieve regenerated from washing.After the TS-1 molecular sieve of inactivation is washed and is dried with pure water, get the crystallizing kettle that 5g puts into 100ml, secondary crystallization solution in crystallizing kettle is the weak aqua ammonia of mass concentration 3%, its pH is 12, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, washing and dry after prepare HTS.Known (the Y of effect from it to chloro propylene epoxidation reaction
eCH=35.68%), molecular sieve catalyst inner duct is not dredged.
Embodiment 1
The fresh TS-1 molecular sieve catalyst S of catalytic reaction first in above-mentioned table 1
eCHbe 99.05, Y
eCHbe 87.43, reacted catalyst only passes through roasting regeneration first, Y in the time of secondary response
eCHbe 84.29.
In the present embodiment, reacted catalyst is after roasting first, again through secondary crystallization regeneration, put into the crystallizing kettle of 100ml by the TS-1 molecular sieve after roasting, secondary crystallization solution in crystallizing kettle is the weak aqua ammonia of 3% mass concentration, and its pH is 12, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, washing and dry after prepare HTS.This S through the composite regenerated TS-1 molecular sieve catalytic secondary response of two steps
eCHbe 99.37, Y
eCHbe 86.27.Obviously be better than only passing through the catalyst activity of roasting.
Embodiment 2
The S of fresh six catalytic reactions of TS-1 molecular sieve catalyst in above-mentioned table 1
eCHbe 99.35, Y
eCHbe that catalyst after 77.41, six secondary responses only passes through roasting regeneration, Y in the time of seven secondary responses
eCHbe 77.16.
In the present embodiment, catalyst after six secondary responses is after roasting, again through secondary crystallization regeneration, put into the crystallizing kettle of 100ml by the TS-1 molecular sieve after roasting, secondary crystallization solution in crystallizing kettle is the weak aqua ammonia of 3% mass concentration, and its pH is 12, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, washing and dry after prepare HTS.This S through composite regenerated TS-1 molecular sieve catalytic the 7th secondary response of two steps
eCHbe 99.41, Y
eCHbe 81.34.Obviously be better than only passing through the catalyst activity of roasting.
Embodiment 3
The present embodiment is identical with all the other conditions of embodiment 1, but after secondary crystallization, has increased calcination steps again.Be that TS-1 molecular sieve after secondary crystallization regeneration obtains regenerated molecular sieve through 550 DEG C of roastings after 5 hours, then this catalyst chloro propylene epoxidation reaction for the second time, gained S
eCHbe 99.43, Y
eCHbe 89.66.Specific activity fresh catalyst activity through the composite regenerated TS-1 molecular sieve catalyst of roasting, secondary crystallization and roasting three steps is slightly high.
Embodiment 4
The present embodiment is identical with all the other conditions of embodiment 2, but after secondary crystallization, has increased calcination steps again.Be that TS-1 molecular sieve after secondary crystallization regeneration obtains regenerated molecular sieve through 550 DEG C of roastings after 5 hours, then the 7th chloro propylene epoxidation reaction of this catalyst, gained S
eCHbe 99.39, Y
eCHbe 86.54.Activity and fresh catalyst through the composite regenerated TS-1 molecular sieve catalyst of roasting, secondary crystallization and roasting three steps are active approaching.
Embodiment 3 and embodiment 4 illustrate, the high-temperature roasting of the 3rd step in composite regenerated, can stable secondary crystallization process in newly-increased avtive spot.
Embodiment 5
The present embodiment is identical with all the other conditions of embodiment 4, and only the secondary crystallization solution condition in regeneration step B is different.The catalyst after six secondary responses is after roasting, again through secondary crystallization regeneration, secondary crystallization solution in crystallizing kettle is ammonium bicarbonate soln, the ammoniacal liquor of dropping 30% is adjusted to 10.5 by secondary crystallization pH, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, prepare the composite regenerated TS-1 molecular sieve of three steps after washing, dry and roasting.The S of this TS-1 molecular sieve catalytic the 7th secondary response
eCHbe 99.28, Y
eCHbe 83.14.
Comparative example 3
This comparative example is identical with all the other conditions of embodiment 4 or 5, and only the secondary crystallization solution condition in regeneration step is different.The catalyst after six secondary responses is after roasting, again through secondary crystallization regeneration, secondary crystallization solution in crystallizing kettle is ammonium sulfate, pH is 6.0, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, prepare the composite regenerated TS-1 molecular sieve of three steps after washing, dry and roasting.The S of this TS-1 molecular sieve catalytic the 7th secondary response
eCHbe 98.64, Y
eCHbe 63.52.
Embodiment 4, embodiment 5 and comparative example 3 have illustrated the impact of secondary crystallization solution on TS-1 regenerating molecular sieve process.Secondary crystallization need to meet specified conditions, just can make TS-1 molecular sieve be regenerated.
Embodiment 6
The present embodiment is similar to embodiment 2, all uses two-step method regeneration TS-1 molecular sieve.Difference is to have supplemented titanium source in the secondary crystallization regenerative process of the present embodiment.The catalyst after six secondary responses is after roasting, again through secondary crystallization regeneration, put into the crystallizing kettle of 100ml by the TS-1 molecular sieve after roasting, secondary crystallization solution in crystallizing kettle is the dilute ammonia solution that is added with 0.2g titanium sulfate, its pH is 12, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, washing and dry after prepare HTS.This S through composite regenerated TS-1 molecular sieve catalytic the 7th secondary response of two steps
eCHbe 99.36, Y
eCHbe 83.56.From catalytic effect, in secondary crystallization actified solution, add titanium source, catalyst activity is more excellent.
Embodiment 7
The present embodiment is similar to embodiment 4, all uses three-step approach regeneration TS-1 molecular sieve.Difference is to have supplemented titanium source in the secondary crystallization regenerative process of the present embodiment.The catalyst after six secondary responses is after roasting, again through secondary crystallization regeneration, put into the crystallizing kettle of 100ml by the TS-1 molecular sieve after roasting, secondary crystallization solution in crystallizing kettle is the dilute ammonia solution that is added with 0.2g titanium sulfate, its pH is 12, under 170 DEG C of conditions, hydrothermal crystallizing 48 hours under sealing self-generated pressure, after filtration, prepare HTS after washing, dry and roasting.This S through composite regenerated TS-1 molecular sieve catalytic the 7th secondary response of three steps
eCHbe 99.32, Y
eCHbe 91.13.
From catalytic effect, in secondary crystallization actified solution, add titanium source, more stable through roasting, the TS-1 molecular sieve catalytic active of three-step approach regeneration is very high, more excellent than the activity of fresh TS-1 catalyst.
Claims (9)
1. a renovation process for titanium-silicon molecular sieve catalyst, is characterized in that, the catalyst of inactivation is composite regenerated through following steps:
Steps A, by the catalyst roasting 2-10 hour of inactivation;
Step B, molecular sieve catalyst after roasting is carried out to secondary crystallization, in the secondary crystallization solution that it is 8-13 that described secondary crystallization refers in pH value, 130-190 DEG C and sealing self-generated pressure under hydrothermal crystallizing 12-120 hour, wherein secondary crystallization solution is the aqueous solution that comprises one or more materials in ammonium salt, ammoniacal liquor and organic amine; Then washing and the dry HTS for preparing regeneration after filtration.
2. renovation process according to claim 1, is characterized in that, in described step B, also comprises titanium sulfate or titanium trichloride as titanium source in secondary crystallization solution.
3. renovation process according to claim 2, is characterized in that, in step B, described titanium source is titanium sulfate.
4. according to the renovation process described in any one in claims 1 to 3, it is characterized in that, in steps A, the catalyst of described inactivation is through repeatedly regeneration and the repeatedly titanium-silicon molecular sieve catalyst of inactivation.
5. renovation process according to claim 1, is characterized in that, in step B, secondary crystallization solution is ammoniacal liquor, and its weight concentration is 0.1-30%.
6. according to the renovation process described in claim 2 or 3, it is characterized in that, in step B, secondary crystallization solution is the mixed liquor in ammoniacal liquor and titanium source, and wherein the weight concentration of ammoniacal liquor is 0.1-30%.
7. renovation process according to claim 6, is characterized in that, described ammoniacal liquor weight concentration is 0.2-10%.
8. renovation process according to claim 7, is characterized in that, described ammoniacal liquor weight concentration is 1-5%.
9. according to the renovation process described in any one in claims 1 to 3, it is characterized in that, the sintering temperature in steps A is 550 DEG C.
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| CN102188994A (en) * | 2011-03-24 | 2011-09-21 | 欧颖 | Method for regenerating titanium silicalite catalyst |
| CN103182322B (en) * | 2011-12-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of method processing deactivated titanium silicon molecular sieve |
| CN103182323B (en) * | 2011-12-29 | 2015-05-20 | 中国石油化工股份有限公司 | Regeneration method of deactivated titanium-silicon molecular sieve catalyst |
| CN103182320B (en) * | 2011-12-29 | 2015-02-25 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve |
| CN105439826B (en) * | 2014-08-25 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of preparation method of propylene glycol monomethyl ether |
| CN105665038B (en) * | 2014-11-20 | 2018-04-06 | 中国石油化工股份有限公司 | Inactivate the renovation process of ethylbenzene catalyst |
| CN105597842B (en) * | 2014-11-20 | 2018-02-13 | 中国石油化工股份有限公司 | The renovation process of ethylbenzene catalyst |
| CN104689848B (en) * | 2015-03-18 | 2017-01-18 | 江苏三吉利化工股份有限公司 | Regeneration method for waste TS-1 titanium silicate molecular sieve |
| CN107537559B (en) * | 2016-06-27 | 2020-08-18 | 中国石油化工股份有限公司 | Titanium-silicon-containing molecular sieve catalyst and preparation method and application thereof |
| CN109718849B (en) * | 2017-10-27 | 2023-04-11 | 中国石油化工股份有限公司 | Regeneration method of deactivated heteroatom molecular sieve and application of regenerated molecular sieve |
| CN109534355A (en) * | 2019-01-30 | 2019-03-29 | 江苏黄马化工有限公司 | A kind of regeneration method of deactivated titanium silicon molecular sieve TS-1 |
| CN109772476B (en) * | 2019-03-18 | 2021-12-03 | 新兴能源科技有限公司 | Method for recovering fine powder of waste molecular sieve catalyst of DMTO device and application |
| CN110075914A (en) * | 2019-05-28 | 2019-08-02 | 江苏扬农化工集团有限公司 | A kind of method of HPPO technique inactive titanium silicon molecule sieve catalyst in-situ regeneration |
| CN111468097B (en) * | 2020-03-24 | 2023-03-03 | 福州大学化肥催化剂国家工程研究中心 | Catalytic cracking catalyst, preparation method and application thereof |
| CN113426494A (en) * | 2021-06-24 | 2021-09-24 | 陕西延长石油（集团）有限责任公司 | Method for reactivating and regenerating waste catalytic cracking catalyst |
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| US7384882B2 (en) * | 2002-05-31 | 2008-06-10 | China Petroleum & Chemical Corporation | Process for regenerating titanium-containing catalysts |
| CN101786638A (en) * | 2009-12-25 | 2010-07-28 | 湘潭大学 | Titanium silicate molecular sieve modification method |
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| IT1314189B1 (en) * | 1999-10-18 | 2002-12-06 | Enichem Spa | PROCEDURE FOR THE REGENERATION OF ZEOLITHIC CATALYSTS CONTAINING TITANIUM |
| CN102188994A (en) * | 2011-03-24 | 2011-09-21 | 欧颖 | Method for regenerating titanium silicalite catalyst |
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| US7384882B2 (en) * | 2002-05-31 | 2008-06-10 | China Petroleum & Chemical Corporation | Process for regenerating titanium-containing catalysts |
| CN101786638A (en) * | 2009-12-25 | 2010-07-28 | 湘潭大学 | Titanium silicate molecular sieve modification method |
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| 氯丙烯环氧化法制环氧氯丙烷催化剂性能研究;陈康庄;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20061115(第11期);B014-187 * |
| 陈康庄.氯丙烯环氧化法制环氧氯丙烷催化剂性能研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2006,(第11期),B014-187. |
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| CN102513152A (en) | 2012-06-27 |
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