CN102188994A - Method for regenerating titanium silicalite catalyst - Google Patents
Method for regenerating titanium silicalite catalyst Download PDFInfo
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- CN102188994A CN102188994A CN2011100717379A CN201110071737A CN102188994A CN 102188994 A CN102188994 A CN 102188994A CN 2011100717379 A CN2011100717379 A CN 2011100717379A CN 201110071737 A CN201110071737 A CN 201110071737A CN 102188994 A CN102188994 A CN 102188994A
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Abstract
The invention relates to a method for regenerating a titanium silicalite catalyst, wherein an inactivated catalyst is complexly regenerated by the following two steps: A: calcining the inactivated catalyst for 2 to 10 hours at the temperature lower than 550 DEG C; B: secondary crystallizing for a calcined molecular sieve, wherein the secondary crystallization is mixing one or a plurality of solutions from ammonium salt, ammoniacal liquor or organic amine, regulating a solution with the pH value from 8 to 13, performing hydrothermal crystallization at the temperature of between 130 and 190 DEG C for 12 to 120 hours under the condition of sealed self-generated pressure, obtaining a regenerated titanium silicalite prepared by filtering, washing and drying. Wherein, preferably a titanium source is supplied in the secondary crystallization solution of the step B. The present invention has the advantages of simple operation and easy controlling process, the activeness of the regenerated titanium silicalite can reach or even exceed a level of a fresh 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 the suction-operated and the shape selective catalysis effect of molecular sieve, has the catalysed oxidn of titanium avtive spot again concurrently, thereby it is widely used in the catalysis hydrogen peroxide and carries out selective oxidation reaction.Be mainly used in catalytic oxidation at present as titanium-silicon molecular sieve TS-1: alkene epoxidation, pure oxidation, partial oxidation of alkanes, phenol hydroxylation, aromatic hydrocarbon epoxidation, ammoxidation of cyclohexanone etc.The above-mentioned oxidation reaction of titanium-silicon molecular sieve TS-1 catalysis has desirable catalytic activity and selectivity of product mostly, thereby but catalyst is easy to inactivation has limited its large-scale commercial Application.
In the prior art, dual mode is generally taked in the regeneration of inactive titanium silicon molecule sieve catalyst, the first is 550 ℃ of following roastings, and another kind of method is to wash under heating up to recover catalyst activity with solvent.As having described a kind of renovation process of titanium-silicon molecular sieve catalyst among the Chinese patent application CN101602011A, wherein the HTS Ti-MWW of inactivation comes from the Ammoximation reaction of epoxidation Reaction of Alkenes and ketone, this method is that the HTS of inactivation is first through the acid compound solution-treated, again through alkaline compound solution hydrothermal treatment consists under 120-200 ℃ self-generated pressure, then after filtration, washing, dry, roasting, the HTS that must regenerate.Wherein said acid compound is one or more in hydrochloric acid, sulfuric acid and the nitric acid; Described alkali compounds is piperidines, hexamethylene imine or its mixture.
In patent US6066750A, a kind of efficient epoxidation process has been described, prepare in the propane at epoxidation of propylene and to use TS-1 as catalyst, use a kind of solvent drip washing TS-1 under the temperature more than 150 ℃ to make its regeneration, this solvent is to contain ammonium or the alkali metal cation amount is the mixed solution of the aliphatic alcohol and water of 10-500ppm.As in isopropyl alcohol and water (6.3: 1), dissolving 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. of 10-500ppm as regenerated solvent.
No matter be roasting regeneration, or the hot regenerated from washing HTS of solvent, its regeneration effect to deactivated molecular sieve is limited, and the high energy of the catalyst after the regeneration returns to the activity level of fresh catalyst.The a plurality of bibliographic data bases in retrieval China and foreign countries find that little deactivation cause to HTS is made research in the prior art, also the report that is not used in combination with solvent wash regeneration about roasting regeneration.
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 two steps.Steps A: with the catalyst of inactivation at 550 ℃ of following roasting 2-10 hours; Step B: the molecular sieve after the roasting is carried out secondary crystallization, wherein said secondary crystallization is meant one or more solution in ammonium salt, ammoniacal liquor or the organic amine is mixed, regulator solution pH value is 8-13, under 130-190 ℃ of condition, under the sealing self-generated pressure hydrothermal crystallizing 12-120 hour, after filtration, prepare the HTS of regeneration after washing and the drying.
The regeneration of catalyst and the inactivation of catalyst are closely connected.General two classes of dividing of the inactivation of molecular sieve catalyst, a class is temporary inactivation, causes the inactivation of duct due to stopping up as accessory substance in the molecular sieve; Another kind of is permanent inactivation, as the loss in catalytic activity site, and mechanical wear, structure is caved in, impurity deposition poisoning etc.The inactivation that occurs on the HTS mainly contains two kinds, and a kind of is that oxidized byproduct stops up molecular sieve pore passage, and another kind is the loss of titanium avtive spot; The a large amount of experiments of inventor's process draw, and the preferred solution that accessory substance stops up on the HTS is roasting, the reparation of the then suitable use secondary crystallization of the loss of titanium avtive spot.
The present invention uses existing roasting regeneration technology, and the secondary crystallization method is applied to the 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 the regeneration can be higher than fresh catalyst.
Use the secondary crystallization method that fresh HTS is carried out modification to improve catalyst activity, as in patent application CN101786638A report being arranged in the prior art.But never this type of method of modifying is made the report of the reason that the 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 the HTS after the crystallization reenters skeleton first, has increased the titanium avtive spot; This content specific embodiment in this article partly describes in detail.The secondary crystallization scheme can remedy the titanium avtive spot that runs off in the deactivated titanium silicon molecular sieve, even can be higher than fresh HTS so that the active sites of regeneration HTS is counted.But the effective prerequisite of secondary crystallization regeneration scheme is that the deactivated titanium silicon molecular sieve inner duct is unimpeded, also promptly needs the deactivated titanium silicon molecular sieve roasting with the mediation duct before secondary crystallization regeneration.
Consider above-mentioned two kinds of inactivations of HTS among the present invention simultaneously, make regeneration back titanium-silicon molecular sieve catalyst activity, even can be higher than the activity of fresh catalyst near the activity of fresh catalyst.
In a preferred embodiment of the present invention, described surviving again is included in step C after the B step, is about to HTS behind the secondary crystallization at 550 ℃ of following roasting 2-10 hours.The roasting of this step can be removed plane of crystal stress, and it is stable to help framework of molecular sieve.
Further preferred, in described regeneration step B, also comprise a certain amount of titanium sulfate or titanium trichloride in the solution of secondary crystallization as the titanium source.More preferably titanium sulfate wherein.
The titanium avtive spot increases on the molecular sieve because of the meaning of secondary crystallization is to make, thereby adds a certain amount of titanium source in secondary crystallization solution, will help forming more titanium avtive spots.In fact,, will cause it to become gel if add too much titanium source in the preparation colloidal sol process before the crystallization first at HTS, thereby to crystallization is totally unfavorable first.And mend titanium in the solution of secondary crystallization is feasible, and the titanium source that replenishes can be aforesaid titanium sulfate or titanium trichloride etc.
Above-mentioned two kinds of titanium sources are compared, more preferably titanium sulfate.No matter be the titanium trichloride of trivalent or the titanium sulfate of tetravalence, can both in secondary crystallization, enter framework of molecular sieve, and the molecular sieve catalytic active that final regeneration obtains is suitable.But because of titanium sulfate is a neutral compound, and titanium trichloride (hydrochloric acid solution that contains titanium trichloride 15%) is a highly acid; Secondary crystallization solution finally needs an alkaline environment, thereby uses titanium sulfate will make that utilization rate of equipment and installations is higher.Equally, compare from toxicity and cost of material aspect, also the preferably sulfuric acid titanium is as the titanium source.
Those skilled in the art will appreciate that among the above-mentioned regeneration step A that the catalyst of described inactivation is through repeatedly regeneration and the repeatedly catalyst of inactivation.That is to say that this decaying catalyst can be before this through the decaying catalyst of repeatedly roasting regeneration or additive method regeneration.
In another preferred embodiment of the present invention, in described regeneration step B, secondary crystallization solution uses ammoniacal liquor, and the weight concentration of ammoniacal liquor is 0.1-30%, and preferred again its concentration is 0.2-10%, and more preferably its concentration is 1-5%.In another preferred embodiment of the present invention, in described regeneration step B, use ammoniacal liquor that the pH value of solution value is adjusted to 10-12, at 170 ℃ of following hydrothermal crystallizings.
Do this selection and come from the optimal conditions of choosing secondary crystallization modification TS-1 molecular sieve and obtain, 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, at first investigated the various effects that contain ammonium salt solution as secondary crystallization solution, the 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 influence of the basicity of secondary crystallization solution, basicity is crossed the low effect that can't produce secondary crystallization; And basicity too high (as pH=13) will cause the little crystal grain corrosion in the TS-1 molecular sieve, and catalyst activity is subjected to certain destruction.This paper points out that also the anion optimum in the secondary crystallization solution is OH
-, and anion such as carbanion, sulfate ion, acetate ion, nitrate ion are all unfavorable to secondary crystallization to a certain extent.Cation in the secondary crystallization solution can be NH
4 +If, but TPA
+Etc. organic then modified effect better (as using TPAOH) of ammonium ion that contains, consider the cost of material factor, weak aqua ammonia does not have the advantage that is suspected to have clearly as secondary crystallization solution.In addition, the cation in the secondary crystallization solution does not preferably comprise Na
+, K
+Deng alkali metal ion,, all will cause framework of molecular sieve to be subjected to very big destruction, even molecular sieve all change the gel state that does not have catalytic activity into as adding amount of NaOH as secondary crystallization solution.
The specific embodiment
Be preferred implementation of the present invention only below, protection scope of the present invention is not limited thereto, and any those skilled in the art can be easy to the change of carrying out or change be encompassed within protection scope of the present invention in technical scope disclosed by the invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
In following examples, be example all, yet those skilled in the art will appreciate that this catalyst recovery process is equally applicable to other HTSs such as TS-2, Ti-MWW and Ti-MCM-41 etc. with the titanium-silicon molecular sieve TS-1.
The preparation of fresh titanium silicalite TS-1: colloid for preparing → crystallization → roasting first → secondary crystallization → roasting promptly gets the fresh titanium silicalite TS-1 after above-mentioned five steps.Described herein fresh titanium silicalite TS-1 is meant through the TS-1 behind the secondary crystallization modification.Concrete synthesis step is: be silicon source, TiCl with the Ludox
3The aqueous solution or Ti (SO4)
2Crystal is that titanium source, TPAOH (TPAOH) are regulated basicity for template agent, ammoniacal liquor; Silicon source, template agent, 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 an amount of TS-1 molecular sieve and make crystal seed and make glue, the 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.With the glue that makes in autoclave under 170 ℃ of spontaneous hydro-thermal pressure crystallization 72h, crystallization product is extremely neutral through the deionized water washing, at 100～120 ℃ of down dry 12～14h,, obtain the TS-1 molecular sieve catalyst of crystallization first then at 550 ℃ of following roasting 6～8h.Under catalyst after the crystallization one or more mixed solutions in ammonium salt, ammoniacal liquor or organic amine, be 8-13 secondary crystallization modification first at pH, modification under 170 ℃ spontaneous hydro-thermal pressure crystallization 24h to 72h; Washing, dry and 550 ℃ 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 the TS-1 activity of molecular sieve catalysts.TS-1 catalysis chloro propylene epoxidation is reflected in the there-necked flask of 250ml-1000ml and carries out, and is equipped with frozen water condensing unit and constant current sampling system, magnetic agitation, water-bath temperature control.The disposable there-necked flask that inserts of certain amount of solvent methyl alcohol, chloropropene, hydrogen peroxide and TS-1 raw material, the primary product of reaction is epoxychloropropane ECH, main accessory substance is a chlorine Isopropanediol monomethyl ether.Use iodometric determination H
2O
2Residual volume and calculate hydrogen peroxide conversion ratio X
H2O2Analyze epoxychloropropane selectivity S with Agilent 6890N gas chromatograph
ECHWith epoxychloropropane once through yield Y
ECH
Use the Y of TS-1 molecular sieve (TS-1 of crystallization and roasting first) the catalysis chloro propylene epoxidation reaction of not passing through the secondary crystallization modification
ECHBe 37.96%; And TS-1 molecular sieve of the same race should react in catalysis behind the secondary crystallization modification, gained Y
ECHBe 87.87%.The inventor explores the reason that above-mentioned catalyst activity significantly promotes with experiment and sign earlier.
At first TS-1 molecular sieve before and after the secondary crystallization is characterized with IR, laser particle size distribution, SEM, XRD and nitrogen absorption.Wherein, the SEM of TS-1 is characterized and laser particle size distributes and characterizes as can be known, grain size, the pattern of the TS-1 of secondary crystallization front and back there is no change; XRD to TS-1 characterizes as can be known, and the degree of crystallinity of the TS-1 before and after the secondary crystallization does not change yet; Nitrogen physical absorption to TS-1 characterizes as can be known, and specific area unanimity, the nitrogen adsorption/desorption spectrogram of the TS-1 before and after the secondary crystallization are in full accord, illustrate that the TS-1 pore passage structure there is no change, and duct quantity does not increase, and the effect in mediation 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 the skeleton, and is to occur in not influence on the titanium of the skeleton structure stability avtive spot.And the IR of TS-1 is characterized as can be known the I of the TS-1 before and after the secondary crystallization
960/ I
800Obviously increase, further specify increasing of titanium avtive spot.
Secondly, the difference of the molecular sieve output in each stage and catalytic activity is analyzed the reason that secondary crystallization can significantly promote the TS-1 catalytic activity from fresh TS-1 molecular sieve catalyst preparation process.Bibliographical information is made elemental analysis with Atomic Emission Spectrometer AES to the TS-1 mother liquor after crystallization first, does not contain titanium elements under TS-1 well-crystallized's situation after the crystallization in the mother liquor.Wherein, the part titanium enters skeleton and forms avtive spot, and we are referred to as the skeleton titanium; Another part titanium then is attached on the skeleton with forms such as load or absorption, and we are referred to as extra-framework titanium.With two batches of different feedstock production TS-1 molecular sieves of titaniferous amount, all the other raw materials are identical, the titanium source of wherein 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 illustrates that also (the comprising skeleton titanium and extra-framework titanium) that exist total titanium amount will be higher than the former on " high titanium TS-1 " molecular sieve.And two kinds of molecular sieves after the crystallization (and roasting) are first carried out the chloro propylene epoxidation reaction and display, the catalytic activity of two kinds of molecular sieves is basic identical, in addition the catalytic activity of " high titanium TS-1 " molecular sieve than " general T S-1 " slightly a little less than.But behind the secondary crystallization modification under the same terms, " high titanium TS-1 " catalyst is obviously than " general T S-1 " catalyst activity height, as the two catalysis chloro propylene epoxidation gained Y
ECHBe respectively 90.80% and 85.24%.
Catalytic reaction activity basically identical after the crystallization first; Explanation is in the latter two skeleton Ti content unanimities of crystallization first, and " high titanium TS-1 " extra-framework titanium content is higher.And the activity of " the high titanium TS-1 " molecular sieve behind the secondary crystallization is obviously higher, illustrates that the extra-framework titanium after the crystallization first reenters the TS-1 skeleton in the secondary crystallization process, illustrates that also secondary crystallization increases the titanium avtive spot of TS-1 molecular sieve.
Above-mentioned experiment and sign illustrate that all the reason that the secondary crystallization modification improves the TS-1 catalytic activity is: under the secondary crystallization condition of high temperature and middle highly basic degree, extra-framework titanium after crystallization is dissolved into certain removable state and is reentered skeleton, and cause increasing of titanium avtive spot, thereby activity of such catalysts promotes obviously.
The present invention is based on above-mentioned theory and makes, and also promptly 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 Examples and embodiment will be used for explanation, adopt roasting regeneration and the method regeneration of deactivated HTS that secondary crystallization regeneration combines in the present invention, can reach desirable regeneration effect.
Comparative Examples 1:
Data in the table 1 are used to illustrate the TS-1 catalyst activity that only passes through roasting regeneration.Each one way reaction condition is that T=30 ℃, t=40min, TS-1 content are 2.37%, n (CH3OH)/n (ALC)=6.5 in the table 1.After each one way reaction just to the roasting regeneration of TS-1 molecular sieve, corresponding seven roastings of seven secondary responses.
Table 1T S-1 is through catalytic perfomance after the roasting regeneration repeatedly
By table 1 data as seen, through after the roasting regeneration repeatedly, the TS-1 molecular sieve catalyst is constant substantially to the selectivity of product epoxychloropropane, but catalyst activity then reduces one by one.This has illustrated that on the one hand roasting regeneration is the means of effectively regenerating, and the slowly loss of titanium avtive spot in the course of reaction has been described on the other hand, thereby roasting need could make that activity of such catalysts returns to higher level in conjunction with other means.
Comparative Examples 2:
Data in this Comparative Examples are used to illustrate the TS-1 catalyst activity of only regenerating with solvent wash, comprising using secondary crystallization solution washing regeneration TS-1 molecular sieve.
Experiment has at first been investigated and has been washed with water, alcohol is washed, acetone washs, three-in-one reagent (isopyknic methyl alcohol, toluene and acetone) is at room temperature and 80 ℃ of following regenerated from washing TS-1 molecular sieves.Even use ultrasonic wave to strengthen mass transfer, still can not obviously recover the TS-1 activity.For example, drop into the reaction of catalysis chloro propylene epoxidation once more after TS-1 molecular sieve filtration, (water) washing and the drying with inactivation, it participates in once more the Y of catalytic reaction
ECHBe 23.15%; And aforementioned TS-1 molecular sieve is with acetone 80 ℃ of heat washings 2 hours in the presence of ultrasonic wave, after filtration, drop into the catalysis chloro propylene epoxidation once more after (water) washing and the drying and react its Y
ECHBe 31.33%.Also be that the accessory substance that stops up in the TS-1 molecular sieve can not discharge easily.
In addition, under the secondary crystallization condition to TS-1 molecular sieve regenerated from washing.With the TS-1 molecular sieve of inactivation with pure water washing and drying after, get the crystallizing kettle that 5g puts into 100ml, secondary crystallization solution in the crystallizing kettle is the weak aqua ammonia of mass concentration 3%, its pH value of solution value is 12, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare HTS after washing and the drying.From it to the effect of chloro propylene epoxidation reaction (Y as can be known
ECH=35.68%), the molecular sieve catalyst inner duct does not obtain mediation.
Embodiment 1:
Fresh TS-1 molecular sieve catalyst in the above-mentioned table 1 is the S of catalytic reaction first
ECHBe 99.05, Y
ECHBe 87.43, reacted first catalyst only passes through roasting regeneration, then Y when secondary response
ECHBe 84.29.
In the present embodiment, reacted first catalyst is through after the roasting, again through secondary crystallization regeneration, TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml, secondary crystallization solution in the crystallizing kettle is the weak aqua ammonia of 3% mass concentration, and its pH value of solution value is 12, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare HTS after washing and the drying.This S through 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 the above-mentioned table 1
ECHBe 99.35, Y
ECHBe that catalyst behind 77.41, six secondary responses only passes through roasting regeneration, Y when seven secondary responses then
ECHBe 77.16.
In the present embodiment, catalyst behind six secondary responses is through after the roasting, again through secondary crystallization regeneration, TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml, secondary crystallization solution in the crystallizing kettle is the weak aqua ammonia of 3% mass concentration, and its pH value of solution value is 12, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare HTS after washing and the drying.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:
Present embodiment is identical with all the other conditions of embodiment 1, but has increased calcination steps behind secondary crystallization again.Be that TS-1 molecular sieve after the secondary crystallization regeneration obtains regenerated molecular sieve through 550 ℃ of roastings after 5 hours, this catalyst chloro propylene epoxidation reaction for the second time then, gained S
ECHBe 99.43, Y
ECHBe 89.66.The specific activity fresh catalyst of composite regenerated TS-1 molecular sieve catalyst is active slightly high through roasting, secondary crystallization and three steps of roasting.
Embodiment 4:
Present embodiment is identical with all the other conditions of embodiment 2, but has increased calcination steps behind secondary crystallization again.Be that TS-1 molecular sieve after the secondary crystallization regeneration obtains regenerated molecular sieve through 550 ℃ of roastings after 5 hours, the 7th chloro propylene epoxidation reaction of this catalyst then, gained S
ECHBe 99.39, Y
ECHBe 86.54.The activity and the fresh catalyst activity of composite regenerated TS-1 molecular sieve catalyst are approaching through roasting, secondary crystallization and three steps of roasting.
Embodiment 3 and embodiment 4 explanations, the high-temperature roasting in the 3rd step in composite regenerated can be stablized avtive spot newly-increased in the secondary crystallization process.
Embodiment 5:
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.Promptly the catalyst behind six secondary responses is through after the roasting, again through secondary crystallization regeneration, secondary crystallization solution in the crystallizing kettle is ammonium bicarbonate soln, the ammoniacal liquor of dropping 30% is adjusted to 10.5 with secondary crystallization pH value of solution value, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare composite regenerated TS-1 molecular sieve of three steps after washing, drying and the roasting.The S of this TS-1 molecular sieve catalytic the 7th secondary response
ECHBe 99.28, Y
ECHBe 83.14.
Comparative Examples 3:
This Comparative Examples is identical with all the other conditions of embodiment 4 or 5, and only the secondary crystallization solution condition in regeneration step is different.Promptly the catalyst behind six secondary responses is through after the roasting, again through secondary crystallization regeneration, secondary crystallization solution in the crystallizing kettle is ammonium sulfate, the pH value of solution value is 6.0, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare composite regenerated TS-1 molecular sieve of three steps after washing, drying and the 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 Examples 3 have illustrated the influence of secondary crystallization solution to TS-1 regenerating molecular sieve process.Secondary crystallization need satisfy specified conditions, just can make the TS-1 molecular sieve obtain regeneration.
Embodiment 6:
Present embodiment is similar to embodiment 2, all uses two-step method regeneration TS-1 molecular sieve.Different is to have replenished the titanium source in the secondary crystallization regenerative process of present embodiment.Promptly the catalyst behind six secondary responses is through after the roasting, again through secondary crystallization regeneration, TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml, secondary crystallization solution in the crystallizing kettle is the dilute ammonia solution that is added with the 0.2g titanium sulfate, its pH value of solution value is 12, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare HTS after washing and the drying.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 as seen, add the titanium source in the secondary crystallization actified solution, the catalyst activity is more excellent.
Embodiment 7:
Present embodiment is similar to embodiment 4, all uses three-step approach regeneration TS-1 molecular sieve.Different is to have replenished the titanium source in the secondary crystallization regenerative process of present embodiment.Promptly the catalyst behind six secondary responses is through after the roasting, again through secondary crystallization regeneration, TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml, secondary crystallization solution in the crystallizing kettle is the dilute ammonia solution that is added with the 0.2g titanium sulfate, its pH value of solution value is 12, under 170 ℃ of conditions, hydrothermal crystallizing 48 hours under the sealing self-generated pressure, after filtration, prepare HTS after washing, drying and the 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 as seen, add the titanium source in the secondary crystallization actified solution, stable through roasting again, the TS-1 molecular sieve catalytic active of three-step approach regeneration is very high, and is more excellent than fresh TS-1 activity of such catalysts.
Claims (10)
1. the renovation process of a titanium-silicon molecular sieve catalyst is characterized in that, the catalyst of inactivation is composite regenerated through following two steps:
A: with the catalyst of inactivation at 550 ℃ of following roasting 2-10 hours;
B: the molecular sieve after the roasting is carried out secondary crystallization, wherein said secondary crystallization is meant one or more solution in ammonium salt, ammoniacal liquor or the organic amine is mixed, regulator solution pH value is 8-13, under 130-190 ℃ of condition, under the sealing self-generated pressure hydrothermal crystallizing 12-120 hour, after filtration, prepare the HTS of regeneration after washing and the drying.
2. the renovation process of titanium-silicon molecular sieve catalyst according to claim 1 is characterized in that, described surviving again is included in step C after the B step, is about to HTS behind the secondary crystallization at 550 ℃ of following roasting 2-10 hours.
3. the renovation process of titanium-silicon molecular sieve catalyst according to claim 1 is characterized in that, in described regeneration step B, also comprises a certain amount of titanium sulfate or titanium trichloride in the solution of secondary crystallization as the titanium source.
4. the renovation process of titanium-silicon molecular sieve catalyst according to claim 2 is characterized in that, in described regeneration step B, also comprises a certain amount of titanium sulfate or titanium trichloride in the solution of secondary crystallization as the titanium source.
5. the renovation process of titanium-silicon molecular sieve catalyst according to claim 3 is characterized in that, in described regeneration step B, described titanium source is a titanium sulfate.
6. according to the renovation process of any described titanium-silicon molecular sieve catalyst in the claim 1 to 5, it is characterized in that in described regeneration step A, the catalyst of described inactivation is through repeatedly regeneration and the repeatedly catalyst of inactivation.
7. according to the renovation process of any described titanium-silicon molecular sieve catalyst in the claim 1 to 5, it is characterized in that in described regeneration step B, secondary crystallization solution uses ammoniacal liquor, the weight concentration of ammoniacal liquor is 0.1-30%.
8. the renovation process of titanium-silicon molecular sieve catalyst according to claim 7 is characterized in that, described ammoniacal liquor weight concentration is 0.2-10%.
9. the renovation process of titanium-silicon molecular sieve catalyst according to claim 8 is characterized in that, described ammoniacal liquor weight concentration is 1-5%.
10. according to the renovation process of any described titanium-silicon molecular sieve catalyst in the claim 1 to 5, it is characterized in that, in described regeneration step B, use ammoniacal liquor that the pH value of solution value is adjusted to 10-12, at 170 ℃ of following hydrothermal crystallizings.
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| CN2011100717379A CN102188994A (en) | 2011-03-24 | 2011-03-24 | Method for regenerating titanium silicalite catalyst |
| CN201110383436.XA CN102513152B (en) | 2011-03-24 | 2011-11-28 | Regeneration method of titanium silicate molecular sieve catalyst |
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| CN201110383436.XA Expired - Fee Related CN102513152B (en) | 2011-03-24 | 2011-11-28 | Regeneration method of titanium silicate molecular sieve catalyst |
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Cited By (10)
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| CN102513152A (en) * | 2011-03-24 | 2012-06-27 | 湘潭大学 | Regeneration method of titanium silicate molecular sieve catalyst |
| CN103182320A (en) * | 2011-12-29 | 2013-07-03 | 中国石油化工股份有限公司 | Regeneration method of titanium-silicon molecular sieve |
| 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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| 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 |
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| IT1314189B1 (en) * | 1999-10-18 | 2002-12-06 | Enichem Spa | PROCEDURE FOR THE REGENERATION OF ZEOLITHIC CATALYSTS CONTAINING TITANIUM |
| WO2003101616A1 (en) * | 2002-05-31 | 2003-12-11 | China Petroleum & Chemical Corporation | A process for regenerating catalyst containing titanium |
| CN101786638B (en) * | 2009-12-25 | 2012-09-05 | 湘潭大学 | Titanium silicate molecular sieve modification method |
| CN102188994A (en) * | 2011-03-24 | 2011-09-21 | 欧颖 | Method for regenerating titanium silicalite catalyst |
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2011
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Also Published As
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| CN102513152B (en) | 2014-10-22 |
| CN102513152A (en) | 2012-06-27 |
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