CN102513152A - Regeneration method of titanium silicate molecular sieve catalyst - Google Patents
Regeneration method of titanium silicate molecular sieve catalyst Download PDFInfo
- Publication number
- CN102513152A CN102513152A CN201110383436XA CN201110383436A CN102513152A CN 102513152 A CN102513152 A CN 102513152A CN 201110383436X A CN201110383436X A CN 201110383436XA CN 201110383436 A CN201110383436 A CN 201110383436A CN 102513152 A CN102513152 A CN 102513152A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- secondary crystallization
- titanium
- catalyst
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
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 the absorption and the shape selective catalysis effect of molecular sieve, have the catalysed oxidn of titanium avtive spot again concurrently, thereby it is widely used in the selective oxidation reaction that the catalysis hydrogen peroxide solution carries out.Be mainly used in the following oxidation reaction of catalysis at present like 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; Another kind method is under heating up, to wash to recover catalyst activity with solvent.As having described a kind of renovation process of titanium-silicon molecular sieve catalyst among the one 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 through 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 10-500ppm 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 NaOH etc. as regenerated solvent.
No matter be roasting regeneration, or solvent thermal regenerated from washing HTS, 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, the report that also is not used in combination with solvent wash regeneration about roasting regeneration.
Summary of the invention
The present invention provides a kind of renovation process of titanium-silicon molecular sieve catalyst, comprises the catalyst of inactivation composite regenerated through following steps: steps A, with the catalyst roasting of inactivation 2-10 hour; Step B; Molecular sieve catalyst after the roasting is carried out secondary crystallization; Said secondary crystallization is meant in the pH value in the secondary crystallization solution of 8-13; 130-190 ℃ with the 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 the organic amine; Then through washing and the dry HTS for preparing regeneration.
In steps A of the present invention, the sintering temperature of using always when said sintering temperature can be those skilled in the art's roasting HTS, for example commonly used is 450～650 ℃, preferred 550 ℃.
The regeneration of catalyst and the inactivation of catalyst are closely connected.The inactivation of molecular sieve catalyst is general to divide two types, and one type is temporary inactivation, causes the inactivation of duct due to stopping up like accessory substance in the molecular sieve; Another kind of is permanent inactivation, like 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 inventor draws through research and experiment, 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 secondary crystallization method (the former modification that is used for fresh catalyst) is applied to the regenerating molecular sieve field, in conjunction with these two kinds of method regeneration HTSs, and has obtained unexpected technique effect.Through 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 gets into skeleton again first, has increased titanium avtive spot (this content will be explained below).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 need be to 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, the said composite regenerated step C that also comprises behind the step B is about to HTS roasting 0.5-10 hour behind the secondary crystallization.The roasting of this step can be removed plane of crystal stress, and it is stable to help framework of molecular sieve.
In step C of the present invention, the sintering temperature of using always when said sintering temperature can be those skilled in the art's roasting HTS, for example commonly used is 450～650 ℃, preferred 550 ℃.
In another preferred embodiment of the present invention, in said step B, also comprise titanium sulfate and/or titanium trichloride in the secondary crystallization solution as the titanium source.The titanium avtive spot increases on the molecular sieve because of the meaning of secondary crystallization is to make, and in secondary crystallization solution, adds a certain amount of titanium source, will help forming more titanium avtive spots.In fact, in preparation fresh titanium silicalite molecular sieve catalyst process,, will cause it to become gel if in the preparation colloidal sol process before the crystallization first, add too much titanium source, thereby to crystallization is totally unfavorable first.And experiment showed, that it is feasible in the solution of secondary crystallization, mending titanium, 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, get into framework of molecular sieve in fact, and the catalytic activity of two kinds of molecular sieves obtaining of final regeneration is suitable.But because of titanium sulfate is a neutral compound, and titanium trichloride (generally using the hydrochloric acid solution that contains titanium trichloride 15%) is 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 in steps A the catalyst of said inactivation can be through repeatedly regeneration and the repeatedly titanium-silicon molecular sieve 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 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%.Again preferably wherein ammonia concn be 0.2-10%, more preferably 1-5%.
In another preferred embodiment of the present invention, the pH value is 10-12 among the step B, and hydrothermal temperature is 160～180 ℃, more preferably 170 ℃.
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, 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 (like pH=13) will cause the little crystal grain corrosion in the TS-1 molecular sieve, and catalyst activity receives 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 the very big destruction of framework of molecular sieve, even molecular sieve all changes the gel that does not have catalytic activity into as adding minor N aOH as secondary crystallization solution.
The specific embodiment
Below be merely preferred implementation of the present invention, 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.
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 process of the silicalite TS-1 of fresh titanium described in the embodiment of the invention is: colloid for preparing → crystallization → roasting first → secondary crystallization → roasting promptly gets the fresh titanium silicalite TS-1 after above-mentioned five steps; That is to say that the fresh titanium silicalite TS-1 described in this paper is meant through the TS-1 behind the secondary crystallization modification.Its concrete synthesis step is: be silicon source, TiCl with the Ludox
3The aqueous solution or Ti (SO
4)
2Crystal is that titanium source, TPAOH (TPAOH) are regulated basicity for template, ammoniacal liquor; Silicon source, template, titanium source and deionized water are added successively according to a certain percentage, after fully stirring, uses ammoniacal liquor adjusting basicity to be 11-13 to pH, add an amount of TS-1 molecular sieve and make crystal seed and process glue, the glue proportioning is following: 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 solution 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 solution 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, can know that to SEM sign and the laser particle size distribution sign of TS-1 grain size, the pattern of the TS-1 before and after the secondary crystallization do not have change; XRD to TS-1 characterizes and can know, 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 and can know, the specific area of the TS-1 before and after the secondary crystallization is consistent, nitrogen adsorption/desorption spectrogram is in full accord, explains that the TS-1 pore passage structure does not have change, and duct quantity does not increase, and the effect in mediation duct is also not obvious; Aforementioned several kinds of signs can explain that the effect of secondary crystallization modification TS-1 can only be to occur on the skeleton, and are to occur on the titanium avtive spot that does not influence skeleton structure stability.And the IR of TS-1 is characterized and can know, the I of the TS-1 before and after the secondary crystallization
960/ I
800Obviously increase, further specify increasing of titanium avtive spot.
Secondly, prepare the molecular sieve output in each stage the process and the difference of catalytic activity is analyzed the reason that secondary crystallization can significantly promote the TS-1 catalytic activity from fresh TS-1 molecular sieve catalyst.Bibliographical information is made elemental analysis with Atomic Emission Spectrometer AES to the TS-1 mother liquor after crystallization first, under TS-1 well-crystallized's situation, does not contain titanium elements after the crystallization in the mother liquor.Wherein, the part titanium gets into 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 explains that also (the comprising skeleton titanium and extra-framework titanium) that on " high titanium TS-1 " molecular sieve, exist total titanium amount will be higher than the former.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 high than " general T S-1 " catalyst activity, like 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 consistent at the latter two skeleton Ti contents 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, explains that the extra-framework titanium after the crystallization first gets into the TS-1 skeleton again in the secondary crystallization process, explains that also secondary crystallization increases the titanium avtive spot of TS-1 molecular sieve.
Above-mentioned experiment and sign explain 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 got into skeleton again; 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 combines the deactivation cause of HTS and secondary crystallization modification to promote the active reason of catalyst, 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 explain 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 1TS-1 is through catalytic perfomance after the roasting regeneration repeatedly
Visible by table 1 data, through after the roasting regeneration repeatedly, the TS-1 molecular sieve catalyst is constant basically to the selectivity of product epoxychloropropane, but catalyst activity then reduces one by one.This has explained 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 combine other means could make that activity of such catalysts returns to higher level.
Comparative Examples 2
Data in this Comparative Examples are used to explain the TS-1 catalyst activity of only regenerating with solvent wash, comprising using secondary crystallization solution washing regeneration TS-1 molecular sieve.
Experiment at first investigated with wash, alcohol is washed, washing with acetone, three-in-one reagent (isopyknic methyl alcohol, toluene and acetone) be 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 washed 2 hours with acetone 80 ℃ of heat in the presence of ultrasonic wave, after filtration, (water) washing and drying, dropped into the reaction of catalysis chloro propylene epoxidation once more, 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%, and its pH value of solution value is 12, under 170 ℃ of conditions; Hydrothermal crystallizing is 48 hours under the sealing self-generated pressure, after filtration, washing and drying, prepares HTS.Can know (Y from its effect to the chloro propylene epoxidation reaction
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 is 48 hours under the sealing self-generated pressure, after filtration, washing and drying, prepares HTS.This S through composite regenerated TS-1 molecular sieve catalytic secondary response of two steps
ECHBe 99.37, Y
ECHBe 86.27.Obviously be superior to 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, 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 weak aqua ammonia of 3% mass concentration, and its pH value of solution value is 12, under 170 ℃ of conditions; Hydrothermal crystallizing is 48 hours under the sealing self-generated pressure, after filtration, washing and drying, prepares 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 superior to only passing through the catalyst activity of roasting.
Embodiment 3
Present embodiment is identical with all the other conditions of embodiment 1, but behind secondary crystallization, has increased calcination steps again.Be that TS-1 molecular sieve after the secondary crystallization regeneration obtains regenerated molecular sieve through 550 ℃ of roastings after 5 hours, then this catalyst for the second time chloro propylene epoxidation react 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 behind secondary crystallization, has increased calcination steps 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 of this catalyst reacts gained S then
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, and 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 is 48 hours under the sealing self-generated pressure, after filtration, washing, drying and roasting, prepares composite regenerated TS-1 molecular sieve of three steps.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, and the pH value of solution value is 6.0, under 170 ℃ of conditions; Hydrothermal crystallizing is 48 hours under the sealing self-generated pressure, after filtration, washing, drying and roasting, prepares composite regenerated TS-1 molecular sieve of three steps.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 been explained 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 with embodiment 2, all uses two-step method regeneration TS-1 molecular sieve.Different is in the secondary crystallization regenerative process of present embodiment, to have replenished the titanium source.Promptly the catalyst behind six secondary responses is through after the roasting; Through secondary crystallization regeneration, the TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml again, and the 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 is 48 hours under the sealing self-generated pressure, after filtration, washing and drying, prepares 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.Visible from catalytic effect, add the titanium source in the secondary crystallization actified solution, the catalyst activity is more excellent.
Embodiment 7
Present embodiment is similar with embodiment 4, all uses three-step approach regeneration TS-1 molecular sieve.Different is in the secondary crystallization regenerative process of present embodiment, to have replenished the titanium source.Promptly the catalyst behind six secondary responses is through after the roasting; Through secondary crystallization regeneration, the TS-1 molecular sieve after the roasting is soon put into the crystallizing kettle of 100ml again, and the 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 is 48 hours under the sealing self-generated pressure, after filtration, washing, drying and roasting, prepares HTS.This S through composite regenerated TS-1 molecular sieve catalytic the 7th secondary response of three steps
ECHBe 99.32, Y
ECHBe 91.13.
Visible from catalytic effect, 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 steps:
Steps A was with the catalyst roasting of inactivation 2-10 hour;
Step B; Molecular sieve catalyst after the roasting is carried out secondary crystallization; Said secondary crystallization is meant in the pH value in the secondary crystallization solution of 8-13; 130-190 ℃ with the 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 the organic amine; Then through washing and the dry HTS for preparing regeneration.
2. renovation process according to claim 1 is characterized in that, the said composite regenerated step C that also comprises behind the step B is about to HTS roasting 0.5-10 hour behind the secondary crystallization.
3. renovation process according to claim 1 and 2 is characterized in that, in said step B, also comprises titanium sulfate and/or titanium trichloride in the secondary crystallization solution as the titanium source.
4. renovation process according to claim 3 is characterized in that, in step B, said titanium source is a titanium sulfate.
5. according to any described renovation process in the claim 1 to 4, it is characterized in that in steps A, the catalyst of said inactivation is through repeatedly regeneration and the repeatedly titanium-silicon molecular sieve catalyst of inactivation.
6. renovation process according to claim 1 and 2 is characterized in that, in step B, secondary crystallization solution is ammoniacal liquor, and its weight concentration is 0.1-30%.
7. renovation process according to claim 3 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%.
8. according to claim 6 or 7 described renovation process, it is characterized in that described ammoniacal liquor weight concentration is 0.2-10%.
9. renovation process according to claim 8 is characterized in that, described ammoniacal liquor weight concentration is 1-5%.
10. according to any described renovation process in the claim 1 to 4, it is characterized in that the pH value is 10-12 among the step B, hydrothermal temperature is 160～180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110383436.XA CN102513152B (en) | 2011-03-24 | 2011-11-28 | Regeneration method of titanium silicate molecular sieve catalyst |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100717379A CN102188994A (en) | 2011-03-24 | 2011-03-24 | Method for regenerating titanium silicalite catalyst |
| CN201110071737.9 | 2011-03-24 | ||
| CN201110383436.XA CN102513152B (en) | 2011-03-24 | 2011-11-28 | Regeneration method of titanium silicate molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102513152A true CN102513152A (en) | 2012-06-27 |
| CN102513152B CN102513152B (en) | 2014-10-22 |
Family
ID=44598394
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100717379A Pending CN102188994A (en) | 2011-03-24 | 2011-03-24 | Method for regenerating titanium silicalite catalyst |
| CN201110383436.XA Expired - Fee Related CN102513152B (en) | 2011-03-24 | 2011-11-28 | Regeneration method of titanium silicate molecular sieve catalyst |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100717379A Pending CN102188994A (en) | 2011-03-24 | 2011-03-24 | Method for regenerating titanium silicalite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN102188994A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689848A (en) * | 2015-03-18 | 2015-06-10 | 江苏三吉利化工股份有限公司 | Regeneration method for waste TS-1 titanium silicate molecular sieve |
| CN109718849A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Inactivate the regeneration method of hetero-atom molecular-sieve and the application of regenerated molecular sieve |
| CN109772476A (en) * | 2019-03-18 | 2019-05-21 | 新兴能源科技有限公司 | A kind of DMTO device catalyst of deposed molecular sieve thin powder recovery method 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 |
| CN111468097A (en) * | 2020-03-24 | 2020-07-31 | 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 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144618C (en) * | 1999-10-18 | 2004-04-07 | 恩尼彻姆公司 | Regeneration method of titanium containing zeolite catalyst |
| 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 |
| CN102188994A (en) * | 2011-03-24 | 2011-09-21 | 欧颖 | Method for regenerating titanium silicalite catalyst |
-
2011
- 2011-03-24 CN CN2011100717379A patent/CN102188994A/en active Pending
- 2011-11-28 CN CN201110383436.XA patent/CN102513152B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1144618C (en) * | 1999-10-18 | 2004-04-07 | 恩尼彻姆公司 | Regeneration method of titanium containing zeolite catalyst |
| 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 |
| CN102188994A (en) * | 2011-03-24 | 2011-09-21 | 欧颖 | Method for regenerating titanium silicalite catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 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》, no. 11, 15 November 2006 (2006-11-15), pages 014 - 187 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104689848A (en) * | 2015-03-18 | 2015-06-10 | 江苏三吉利化工股份有限公司 | Regeneration method for waste TS-1 titanium silicate molecular sieve |
| CN109718849A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Inactivate the regeneration method of hetero-atom molecular-sieve and the application of regenerated molecular sieve |
| 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 |
| CN109772476A (en) * | 2019-03-18 | 2019-05-21 | 新兴能源科技有限公司 | A kind of DMTO device catalyst of deposed molecular sieve thin powder recovery method 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 |
| CN111468097A (en) * | 2020-03-24 | 2020-07-31 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102513152B (en) | 2014-10-22 |
| CN102188994A (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102513152B (en) | Regeneration method of titanium silicate molecular sieve catalyst | |
| CN101786638B (en) | Titanium silicate molecular sieve modification method | |
| CN111943224B (en) | Preparation method of Cu-SSZ-13 molecular sieve catalyst, obtained product and application | |
| CN101757945A (en) | Titanium-silicon molecular sieve TS-1 catalyst for catalyzing ketone oximation reaction | |
| CN101850986B (en) | Method for modifying titanium-silicalite | |
| CN101767036A (en) | Titanium silicalite TS-1 catalyst preparation method | |
| CN101327934B (en) | Preparation of titanium silicon molecular sieve having MFI structure | |
| CN103183355B (en) | Precious metal modification method of titanium silicalite molecular sieve | |
| CN102502690A (en) | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base | |
| CN104707648B (en) | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve | |
| CN103182323B (en) | Regeneration method of deactivated titanium-silicon molecular sieve catalyst | |
| CN103182322B (en) | A kind of method processing deactivated titanium silicon molecular sieve | |
| CN103708496A (en) | HZSM-5@silicalite-1 core-shell structure molecular sieve, and preparation method and application thereof | |
| CN105251528A (en) | Method for one-step synthesis of Cu-CHA catalyst with mixture of tetraethylammonium hydroxide and copper ammonia complex as templating agent | |
| CN103818924A (en) | Preparation method of titanium-silicon molecular sieve and application | |
| CN106006665A (en) | Method for preparing titanium silicalite molecular sieve TS-1 | |
| CN106694027B (en) | A kind of amine oxidation prepares the preparation and its application of the transition-metal catalyst of oxime | |
| CN104229820A (en) | Method for preparing TS-1 titanium silicalite molecular sieve | |
| CN104709919A (en) | Tin-containing molecular sieve with MWW topological structure and preparation and application thereof | |
| CN105314649B (en) | A kind of tin si molecular sieves, preparation method and application | |
| CN112875720B (en) | Method for preparing aluminum pair-enriched SSZ-13 molecular sieve and application thereof | |
| CN101683984B (en) | Method for synthesizing titanium silicon materials containing noble metal | |
| CN104512906B (en) | Titanium-silicon molecular sieve and preparation method thereof | |
| CN100443408C (en) | Gas solid phase preparation method of high performance titanium silicon zeolite | |
| CN105293517B (en) | HTS and its preparation method and application and a kind of method of alkene direct oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141022 Termination date: 20201128 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |