CN1461671A - Method for regeneration of titaniferous catalyst - Google Patents
Method for regeneration of titaniferous catalyst Download PDFInfo
- Publication number
- CN1461671A CN1461671A CN 03137913 CN03137913A CN1461671A CN 1461671 A CN1461671 A CN 1461671A CN 03137913 CN03137913 CN 03137913 CN 03137913 A CN03137913 A CN 03137913A CN 1461671 A CN1461671 A CN 1461671A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- accordance
- titanium
- acid
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for regenerating the deactivated Ti-contained catalyst includes such steps as treating in acidic solution (pH is less than or equal to 3), drying and calcining. Its advantages are simple process and high effect to restore original activity, selectivity and stability.
Description
Technical field
The invention relates to a kind of renovation process of catalyst, further say so about the renovation process of titanium-containing catalyst in a kind of carbonyls amidoximeization or the nitrilo compound oxidation reaction.
Background technology
Carbonyls and azanol reaction are the main method of synthetic corresponding oxime compound.For example, cyclohexanone oxime is a key intermediate of producing epsilon-caprolactams, and caprolactam is important Organic Chemicals, mainly is used as the monomer of synthetic fibers and engineering plastics (as nylon-6).Industrial about 91% caprolactam is produced through the cyclohexanone oxime route, i.e. cyclohexanone-azanol technology.This process not only complex process, production procedure is long, equipment investment is high, and because of producing or use NO
x, SO
xDeng and have more serious corrosion and a pollution problem.
Early eighties, Italy Taramasso is in USP 4410501, a kind of new catalytic material-HTS is disclosed, it has good selective oxidation to hydrocarbon, alcohol, phenol etc., and (EP 0230949, USP 4480135, USP 4396783), it is applied to the oxidation of phenol preparing benzenediol and has realized industrialization.
EP 0208311, EP 0267362, EP 0496385, EP 0564040 etc. have reported in succession under titanium molecular sieve catalysis, carry out Ammoximation reaction one by cyclohexanone and ammonia, hydrogen peroxide and go on foot the method for preparing cyclohexanone oxime.This method reaction condition gentleness, target product yield height, and have characteristics such as technical process is simple, plant investment is few, the three wastes are few, environmentally friendly.
In addition, other titaniferous catalysis material application in amidoximeization also has report.For example, reported that in EP0347926 the titanium oxide to be carried on the silica is the cyclohexanone oxamidinating reaction of catalyst; J.Le Bars etc. are at Appl.Catal.A 136 (1996) P69, and P.Wu etc. have also reported the Ammoximation reaction to multiple aldehyde, ketonic compound such as other types of molecules sieve (as Ti-ZSM-48, Ti-β, Ti-MOR) of containing Ti in p.400 at J.Catal.168 (1997).
Nitrilo compound and hydroperoxidation are the main method of synthetic corresponding azanol, have reported HTS or the titaniferous amorphous catalyst oxidation reaction to nitrilo compound (as secondary amine, ammonia etc.) in USP4918194, USP 5320819.
Along with progressively going deep into of catalytic reaction research, titanium-containing catalyst, the particularly HTS stability problem in the reaction of cyclohexanone oxamidinating synthesizing cyclohexane 1 ketoxime draws attention.EP 0496385 report needs in the course of reaction to adopt the method for regularly taking out decaying catalyst and replenishing fresh dose, just can keep desirable catalytic activity.The stability that how to prolong HTS has become the focus that people pay close attention to.
USP 4794198 discloses catalyst has been carried out pretreated method, can improve selectivity like this, helps to prolong stability.P.Roffia etc. propose in p.43 by optimizing process conditions at Stud.Surf.Sci.Catal.55 (1990), as select suitable solvent, improve catalyst concn and reaction temperature, come the fortifying catalytic reaction rate, reduce uncatalyzed reaction.But the stability that prolongs catalyst by said method is limited, because the cost of HTS is higher, how utilizing behind its inactivation, how regenerating is the problem that must solve.
Usually, the renovation process of decaying catalyst has two kinds: solvent wash and roasting.At Selective Oxidation by Heterogeneous Catalysis (2001, p.112) in the book, the deactivation cause of pointing out HTS in the cyclohexanone oxamidinating reaction has three: the dissolving of (1) silicon, the migration of (2) titanium, (3) accessory substance plug-hole, and further point out to adopt the method for tert-butyl alcohol washing that the decaying catalyst that the accessory substance plug-hole causes is regenerated, but activity only can partly be recovered, and the catalyst regeneration effect is unsatisfactory.
A kind of renovation process that discloses among the CN 1302693A is the catalyst of calcining in advance, under the situation that inorganic fluoride exists, handles with hydrogen peroxide in water-bearing media, and then heat-treats.Be that the regenerative process for preparing catalyst in the cyclohexanone oxime with cyclohexanone oxamidinating is that example describes in this method, the regenerative agent activity is the highest return to fresh dose 84%, if and point out the only regeneration of the method by heat treatment (550 ℃ of roastings) of catalyst, regenerative agent activity only return to fresh dose 31%.But the activity that adopts this method regenerative agent still fails to return to fully fresh dose of level, and uses easy toxigenous fluoride in this method chemical treatment, has certain harmfulness.
CN 1290194A discloses a kind of renovation process of catalyst, its essence is a kind of regeneration based on the catalyst of load gold on titanium dioxide or the hydrated titanium dioxide carrier, detailed process is described catalyst to be contacted its catalytic activity of regenerating with water or with diluted acid or with Dilute Hydrogen Peroxide Solution.Catalyst described in the patent adopts the preparation of " deposition-precipitation " method, is used at gas phase oxidation unsaturated hydrocarbons; Described diluted acid pH is 4~7.5, the dilute sulfuric acid or the hydrofluoric acid of preferred pH5.5~6.With the propylene oxidation reaction is example, adopts this patented method, the regenerative agent activity is the highest return to fresh dose 80%, fail to return to fully fresh dose of level, also the stability of not mentioned regenerative agent how.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of regenerative agent can return to fresh dose the level and the renovation process of the titanium-containing catalyst of good stability.
The renovation process of titanium-containing catalyst provided by the invention is to handle decaying catalyst, drying and roasting then in the acid solution of pH≤3, preferred pH≤1.
More particularly, method provided by the invention is to handle decaying catalyst in the acid solution of pH≤3, preferred pH≤1, wherein the concentration of catalyst in acid solution is 1~20 weight %, is preferably 3~15 weight %, treatment conditions are to descend drying and roasting then 0.5~6 hour, preferred 1~4 hour at 50~100 ℃, preferred 70~90 ℃.
In renovation process provided by the invention, said acid solution is selected from a kind of in the inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, also can be the mixed liquor of aforementioned inorganic acid and hydrogen peroxide, the concentration of hydrogen peroxide is 0~10 weight % in mixed liquor, preferred 0~5 weight %.
Said titanium-containing catalyst can be the compound catalyze material of HTS or load titanium, said HTS is former powder form or shaped form, is selected from one of TS-1, TS-2, Ti-ZSM-5, Ti-ZSM-12, Ti-ZSM-48, Ti-β, Ti-MCM-41 and Ti-MOR.
Renovation process provided by the present invention is particularly useful in the oxidation reaction of the Ammoximation reaction of carbonyls or nitrilo compound the regeneration of the titanium-containing catalyst of inactivation.
Said carbonyls can be cyclohexanone, acetone, MEK, cyclopentanone, right-hydroxy acetophenone, acetophenone, ring 12 carbon ketone, furfural, benzaldehyde or p-tolyl aldehyde etc., and nitrilo compound is secondary amine and ammonia etc.
The renovation process of titanium-containing catalyst provided by the invention, regeneration effect is remarkable, and the activity of regenerative agent, selectivity and stability all can return to fresh dose level, and can repeatedly regenerate, use, thereby improved the utilization rate of catalyst greatly, reduced catalyst consumption.
In addition, in the method provided by the invention, do not use easy toxigenous fluoride, raw material is cheap and easy to get, and technological operation is easy.
The specific embodiment
Below by embodiment the present invention will be further described.
In following embodiment and Comparative Examples, used HTS (TS-1) is built long joint-stock company by Yueyang and is produced; Cyclohexanone (purity 〉=99.5%) is provided by the Beijing Chemical Plant, and hydrogen peroxide (contains H
2O
227.5 weight %) provide by the Tianjin factory that orientalizes; Ammonia (purity 〉=99.9%) is provided by test chemical plant, Beijing; The tert-butyl alcohol (contain the tert-butyl alcohol 86.5 weight %, all the other are water and small amount of impurities) is provided by the smooth-going chemical industry in Beijing Co., Ltd, and other used all ingredients are all provided chemical pure if no special instructions by the Beijing Chemical Plant.
The regeneration effect of catalyst draws by estimation of stability.
Continous way slurry-bed reaction device is adopted in the catalyst stability evaluation, reactor volume 150ml, magnetic agitation, oil bath heating.Reaction raw materials and the product reactor of being back to back, catalyst is tackled in reactor.Product is formed with gc analysis, and hydrogen peroxide conversion obtains with its content of iodometric determination.
For estimating out in a short time the stability of catalyst, the comparatively responsive deactivation processes condition of accelerating is adopted in evaluation test, promptly compare with the optimization process conditions, under higher charging air speed, lower temperature and catalyst concn, estimate, the result that this condition evaluating goes out is representative, the quality of regeneration effect can be described, but on the absolute figure and be not equal to the stability data of optimizing catalyst under the process conditions.
Technological parameter is as follows in the evaluation test of embodiment 1~5 and Comparative Examples 1~3, H
2O
2: cyclohexanone=1.10: 1 (mol ratio), ammonia: cyclohexanone=1.70: 1 (mol ratio), the tert-butyl alcohol: cyclohexanone=3.30: 1 (mol ratio), catalyst concn is 1.8 weight %, the material mean residence time is 72 minutes, and reaction temperature is 76 ± 1 ℃, and pressure is normal pressure.
The catalyst steady running time is in the one way duration of runs of cyclohexanone conversion ratio 〉=97%.
Adopt fresh catalyst to carry out estimation of stability, the results are shown in Table 1.
Embodiment 1
Used decaying catalyst is that fresh catalyst is through the inactivation sample of evaluation test steady running after 40 hours.
4.5 gram inactivation samples are mixed with 90 grams, 5% rare nitric acid, in 85 ℃ of stirrings 2 hours, filter, solid washes repeatedly with deionized water, after 120 ℃ of dryings, in 560 ℃ of roastings 6 hours, obtains regenerated catalyst.
Above-mentioned regenerated catalyst is carried out estimation of stability, the results are shown in Table 1.
Embodiment 2
Used decaying catalyst is the regenerated catalyst among the embodiment 1, through 42 hours inactivation sample of steady running, promptly same catalyst is carried out the regeneration test second time again.
Renovation process is with embodiment 1, and estimation of stability the results are shown in Table 1.
Comparative Examples 1
The used decaying catalyst of this Comparative Examples is identical with embodiment 1.
Difference from Example 1 is that decaying catalyst is handled without acid solution, and convection drying, roasting obtain regenerated catalyst, and estimation of stability the results are shown in Table 1.
Comparative Examples 2
The used decaying catalyst of this Comparative Examples is identical with embodiment 1.
Difference from Example 1 is that decaying catalyst carries out acid solution processing and roasting (method is with embodiment 1) again and obtains regenerated catalyst earlier through roasting, and estimation of stability the results are shown in Table 1.
Comparative Examples 3
The used decaying catalyst of this Comparative Examples is identical with embodiment 1.
4.0 gram inactivation samples are mixed with 200 gram 0.0005% dilute sulfuric acids (pH is 4), stirred filtration 3 hours in 70 ℃, solid washes repeatedly with deionized water, after 120 ℃ of dryings, in 560 ℃ of roastings 6 hours, obtain regenerated catalyst, its estimation of stability the results are shown in Table 1.
Table 1
Numbering | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Embodiment 1 | Embodiment 2 | |
The catalyst original state | Fresh dose | Inactivation behind the running 40h | Inactivation behind the running 40h | Inactivation behind the running 40h | Inactivation behind the running 40h | Regeneration once after, revalue the running 42h after inactivation |
Regeneration | - | Roasting | Elder generation's roasting, acid treatment and roasting again | Acid treatment and roasting | Acid treatment and roasting | Acid treatment and roasting |
Evaluation result | ||||||
Cyclohexanone conversion ratio % | 98.5 | 98.4 | 98.4 | 98.6 | 98.6 | 98.6 |
H 2O 2Conversion ratio % | 100 | 100 | 100 | 100 | 100 | 100 |
Ketone is to cyclohexanone oxime selectivity % | 99.7 | 99.6 | 99.7 | 99.7 | 99.7 | 99.7 |
H 2O 2To cyclohexanone oxime selectivity % | 89.3 | 89.1 | 89.1 | 89.4 | 89.4 | 89.4 |
Catalyst steady running time h | 40 | 30 | 31 | 33 | 42 | 41 |
As can be seen from Table 1: only adopt the method (Comparative Examples 1) of roasting or adopt first roasting, acid solution is handled and method (Comparative Examples 2) regenerated catalyst of roasting again, though the activity of regenerative agent, selectivity can be recovered, its stability does not return to fresh dose level; And the employing acid solution is handled and the method regenerated catalyst of roasting, if acid concentration low excessively (pH is 4) (Comparative Examples 3), also can not obtain desirable regeneration effect, and adopt method of the present invention, the activity of regenerative agent, selectivity, stability all can return to fresh dose of level (embodiment 1), and (embodiment 2) can repeatedly be regenerated, be used to catalyst.
Embodiment 3
Used decaying catalyst is identical with embodiment 1.
Inactivation sample 4.5 grams are mixed with 40 grams, 3% watery hydrochloric acid, 5 grams, 27.5 weight % hydrogen peroxide, stirred filtration 2 hours in 75 ℃, solid washes repeatedly with deionized water, after 120 ℃ of dryings, in 560 ℃ of roastings 6 hours, obtain regenerated catalyst, its estimation of stability the results are shown in Table 2.
Embodiment 4
Used decaying catalyst is identical with embodiment 1.
Inactivation sample 4.5 grams are mixed with 90 grams, 10% phosphoric acid,diluted, 5 grams, 27.5 weight % hydrogen peroxide, stirred filtration 1 hour in 80 ℃, solid washes repeatedly with deionized water, after 120 ℃ of dryings, in 560 ℃ of roastings 6 hours, obtain regenerated catalyst, its estimation of stability the results are shown in Table 2.
Embodiment 5
Used fresh catalyst is identical with embodiment 1, then difference under the optimized process conditions scope, the inactivation sample of steady running after 400 hours.
Above-mentioned inactivation sample 150 grams are mixed with 1000 grams, 5% rare nitric acid, in 90 ℃ of stirrings 3 hours, filter, solid washes repeatedly with deionized water, after 120 ℃ of dryings, in 560 ℃ of roastings 6 hours, obtains regenerated catalyst, and its estimation of stability the results are shown in Table 2.
Table 2
Numbering | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
The catalyst original state | Fresh dose | Inactivation behind the running 40h | Inactivation behind the running 40h | Inactivation behind the running 400h |
Regeneration | ----- | Hydrochloric acid+H 2O 2Handle roasting | Phosphoric acid+H 2O 2Handle roasting | The nitric acid treatment roasting |
Evaluation result | ||||
Cyclohexanone conversion ratio % | 98.5 | 98.4 | 98.4 | 98.6 |
?H 2O 2Conversion ratio % | 100 | 100 | 100 | 100 |
Ketone is to cyclohexanone oxime selectivity % | 99.7 | 99.6 | 99.5 | 99.7 |
?H 2O 2To cyclohexanone oxime selectivity % | 89.3 | 89.1 | 89.0 | 89.4 |
Catalyst steady running time h | 40 | 39 | 38 | 42 |
As can be seen from Table 2, the activity of regenerative agent, selectivity, stability all can return to fresh dose of level.
Embodiment 6~9
With Ti-MOR (Si/Al=300, with the p.400 method preparation of middle record of J.Catal.168 (1997)) be catalyst, embodiment 6~9 is respectively to be the process that raw material and ammonia, hydrogen peroxide carry out Ammoximation reaction with acetone, cyclopentanone, benzaldehyde, p-tolyl aldehyde, with water is solvent, the evaluation test process conditions are as follows, H
2O
2: ketone (aldehyde)=1.15: 1 (mol ratio), ammonia: ketone (aldehyde)=2.0: 1 (mol ratio), water: ketone (aldehyde)=8: 1 (volume ratio), catalyst concn is 3.0 weight %, the material mean residence time is 120 minutes, and reaction temperature is 60+1 ℃, and pressure is normal pressure.
Get the decaying catalyst of above-mentioned reaction and regenerate, regeneration condition is with embodiment 1.
Catalyst after the regeneration is carried out estimation of stability, and among these embodiment, the said steady running time is in the one way duration of runs of conversion ratio 〉=90%.
The results are shown in Table 3.
Comparative Examples 4~7
Comparative Examples 4~7, catalyst system therefor and evaluation response be with embodiment 6~9, and difference is that decaying catalyst handles without acid solution, and convection drying, roasting obtain regenerated catalyst.
Estimation of stability the results are shown in Table 3.
Embodiment 10
Catalyst system therefor is the TS-1 molecular sieve, and fresh dose with embodiment 1, reacts the oxidation reaction for diethylamine and hydrogen peroxide, is solvent with the tert-butyl alcohol, and the evaluation test process conditions are as follows, H
2O
2: amine=1.1: 1 (mol ratio), the tert-butyl alcohol: amine=5: 1 (mol ratio), catalyst concn are 2.5 weight %, and the material mean residence time is 60 minutes, and reaction temperature is 80+1 ℃, and pressure is normal pressure.
Get the decaying catalyst of above-mentioned reaction and regenerate, regeneration condition is with embodiment 1.
Catalyst after the regeneration is carried out estimation of stability, and the steady running time the results are shown in Table 3 in the one way duration of runs of conversion ratio 〉=90%.
Comparative Examples 8
This Comparative Examples catalyst system therefor and evaluation response be with embodiment 10, and difference is that decaying catalyst handles without acid solution, and convection drying, roasting obtain regenerated catalyst.
Estimation of stability the results are shown in Table 3.
Embodiment 11
Adopt the silicon oxide catalyst (preparation method is with EP0347926 embodiment 6) of load titanium, the reaction of catalysis of pimelinketone and ammonia, hydrogen peroxide, the evaluation test process conditions are with embodiment 1.
The decaying catalyst that negate is answered is regenerated, and regeneration condition is with embodiment 1.
Catalyst after the regeneration is carried out estimation of stability, the results are shown in Table 3.
Comparative Examples 9
Catalyst system therefor and evaluation response thereof be with embodiment 11, and difference is that decaying catalyst handles convection drying and roasting without acid solution.Estimation of stability the results are shown in Table 3.
Table 3
Numbering | Reactant | Regeneration | Catalyst steady running time % (comparing) with fresh dose |
Embodiment 6 | Acetone | Acid treatment and roasting | ????105 |
Embodiment 7 | Cyclopentanone | Acid treatment and roasting | ????98 |
Embodiment 8 | Benzaldehyde | Acid treatment and roasting | ????90 |
Embodiment 9 | P-tolyl aldehyde | Acid treatment and roasting | ????95 |
Embodiment 10 | Diethylamine | Acid treatment and roasting | ????95 |
Embodiment 11 | Cyclohexanone | Acid treatment and roasting | ????96 |
Comparative Examples 4 | Acetone | Roasting | ????75 |
Comparative Examples 5 | Cyclopentanone | Roasting | ????70 |
Comparative Examples 6 | Benzaldehyde | Roasting | ????65 |
Comparative Examples 7 | P-tolyl aldehyde | Roasting | ????70 |
Comparative Examples 8 | Diethylamine | Roasting | ????65 |
Comparative Examples 9 | Cyclohexanone | Roasting | ????70 |
As can be seen from Table 3, Comparative Examples adopts the method regenerated catalyst of roasting, the stability of regenerative agent only return to fresh dose 65~75%, and adopt method provided by the invention, the stability of regenerative agent all can return to fresh dose of level substantially.
Claims (14)
1, a kind of renovation process of titanium-containing catalyst is characterized in that this method is to handle decaying catalyst in the acid solution of pH≤3, drying and roasting then.
According to the said method of claim 1, it is characterized in that 2, the concentration of decaying catalyst in acid solution is 1~20 weight %, handle and under 50~100 ℃, carried out 0.5~6 hour.
According to the said method of claim 2, it is characterized in that 3, the concentration of decaying catalyst in acid solution is 3~15 weight %, handle and under 70~90 ℃, carried out 1~4 hour.
4, in accordance with the method for claim 1, it is characterized in that said titanium-containing catalyst is a HTS.
5, in accordance with the method for claim 1, it is characterized in that said titanium-containing catalyst is the compound catalyze material of load titanium.
6, in accordance with the method for claim 4, it is characterized in that said HTS is selected from one of TS-1, TS-2, Ti-ZSM-5, Ti-ZSM-12, Ti-ZSM-48, Ti-β, Ti-MCM-41 and Ti-MOR.
7, in accordance with the method for claim 4, it is characterized in that said HTS is the form of former powder or the form of moulding.
8, in accordance with the method for claim 1, it is characterized in that said acid solution is the mixed liquor of inorganic acid and hydrogen peroxide, concentration 0~10 weight % of hydrogen peroxide in the mixed liquor.
9, in accordance with the method for claim 8, it is characterized in that said inorganic acid is selected from a kind of in nitric acid, sulfuric acid, hydrochloric acid and the phosphoric acid.
10, in accordance with the method for claim 8, the concentration that it is characterized in that hydrogen peroxide in the said mixed liquor is 0~5 weight %.
11, in accordance with the method for claim 1, it is characterized in that said titanium-containing catalyst is a carbonyls amidoxime catalyst.
12, in accordance with the method for claim 11, it is characterized in that said carbonyls is selected from a kind of of cyclohexanone, acetone, MEK, cyclopentanone, right-hydroxy acetophenone, acetophenone, ring 12 carbon ketone, furfural, benzaldehyde and p-tolyl aldehyde.
13, in accordance with the method for claim 1, it is characterized in that said titanium-containing catalyst is the nitrilo compound oxidation catalyst.
14, in accordance with the method for claim 1, pH≤1 that it is characterized in that said acid solution.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 03137913 CN1212195C (en) | 2002-05-31 | 2003-05-30 | Method for regeneration of titaniferous catalyst |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN02120784.4 | 2002-05-31 | ||
CN02120784 | 2002-05-31 | ||
CN 03137913 CN1212195C (en) | 2002-05-31 | 2003-05-30 | Method for regeneration of titaniferous catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1461671A true CN1461671A (en) | 2003-12-17 |
CN1212195C CN1212195C (en) | 2005-07-27 |
Family
ID=29780932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 03137913 Expired - Lifetime CN1212195C (en) | 2002-05-31 | 2003-05-30 | Method for regeneration of titaniferous catalyst |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1212195C (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101237928B (en) * | 2005-07-27 | 2011-05-18 | Sk能源株式会社 | Method of regeneration of titanium-containing molecular sieve catalyst |
CN101786638B (en) * | 2009-12-25 | 2012-09-05 | 湘潭大学 | Titanium silicate molecular sieve modification method |
CN102824926A (en) * | 2012-09-03 | 2012-12-19 | 中国天辰工程有限公司 | Regeneration method of inactivated titanium silicon molecular sieve |
CN102974393A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
CN104512906A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and preparation method thereof |
CN109251193A (en) * | 2017-07-12 | 2019-01-22 | 中国石油化工股份有限公司 | The method for preparing propene carbonate |
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 |
CN111389454A (en) * | 2020-04-29 | 2020-07-10 | 陕西延长石油(集团)有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
CN114308118A (en) * | 2022-01-05 | 2022-04-12 | 江苏扬农化工集团有限公司 | In-situ regeneration method of titanium-silicon molecular sieve |
CN114308117A (en) * | 2022-01-05 | 2022-04-12 | 江苏扬农化工集团有限公司 | Method for in-situ iron removal of titanium-silicon molecular sieve |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101439299B (en) * | 2007-11-22 | 2013-03-27 | 中国石油化工股份有限公司 | Catalyst regeneration process |
CN101455981B (en) * | 2007-12-13 | 2012-01-25 | 中国石油化工股份有限公司 | Improved titanium-containing catalyst regeneration method |
-
2003
- 2003-05-30 CN CN 03137913 patent/CN1212195C/en not_active Expired - Lifetime
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101237928B (en) * | 2005-07-27 | 2011-05-18 | Sk能源株式会社 | Method of regeneration of titanium-containing molecular sieve catalyst |
CN101786638B (en) * | 2009-12-25 | 2012-09-05 | 湘潭大学 | Titanium silicate molecular sieve modification method |
CN102824926A (en) * | 2012-09-03 | 2012-12-19 | 中国天辰工程有限公司 | Regeneration method of inactivated titanium silicon molecular sieve |
CN102974393A (en) * | 2012-11-21 | 2013-03-20 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
CN102974393B (en) * | 2012-11-21 | 2014-10-15 | 西安近代化学研究所 | Regeneration method for modified zeolite molecular sieve amination catalyst |
CN104512906B (en) * | 2013-09-29 | 2017-05-24 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and preparation method thereof |
CN104512906A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve and preparation method thereof |
CN109251193A (en) * | 2017-07-12 | 2019-01-22 | 中国石油化工股份有限公司 | The method for preparing propene carbonate |
CN109251193B (en) * | 2017-07-12 | 2024-07-09 | 中国石油化工股份有限公司 | Method for preparing propylene carbonate |
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 |
CN111389454A (en) * | 2020-04-29 | 2020-07-10 | 陕西延长石油(集团)有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
CN111389454B (en) * | 2020-04-29 | 2022-09-20 | 陕西延长石油(集团)有限责任公司 | Catalyst and method for preparing p-tolualdehyde from synthesis gas and toluene |
CN114308118A (en) * | 2022-01-05 | 2022-04-12 | 江苏扬农化工集团有限公司 | In-situ regeneration method of titanium-silicon molecular sieve |
CN114308117A (en) * | 2022-01-05 | 2022-04-12 | 江苏扬农化工集团有限公司 | Method for in-situ iron removal of titanium-silicon molecular sieve |
Also Published As
Publication number | Publication date |
---|---|
CN1212195C (en) | 2005-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1212195C (en) | Method for regeneration of titaniferous catalyst | |
CN1868988A (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
CN1273443C (en) | Method for preparing oxime by using ammonium salt or substituted ammonium salt through cocatalysis | |
CN103182322B (en) | A kind of method processing deactivated titanium silicon molecular sieve | |
JPH07247230A (en) | Production of alkanone and/or alkanol | |
CN101039892A (en) | Catalysts for cycloalkanes oxidation and decomposition of cycloalkyl hydroperoxide | |
CN105665002A (en) | Method for regenerating deactivated titanium silicon molecular sieve catalyst | |
JP4772326B2 (en) | Method for regenerating titanium-containing catalyst | |
CN1414937A (en) | Method for producing alcohol/ketone mixtures | |
CN101591024A (en) | A kind of method of modifying of HTS | |
CN101367709A (en) | Method for catalysis of atmospheric oxidation cyclohexane with ultra-fine A100H-supported metalloporphyrin | |
CN101439299B (en) | Catalyst regeneration process | |
CN101186601A (en) | Method for catalyzing cyclone oxide to synthesizing lactone by using nano magnesium-base catalyst | |
CN109126864A (en) | The regeneration method of inactive titanium silicon molecule sieve catalyst | |
CN101429149A (en) | Method for producing Epsilon-hexanolactam with cyclohexanone oxime gas-phase beckmann rearrangement | |
CN102824926A (en) | Regeneration method of inactivated titanium silicon molecular sieve | |
CN1246301C (en) | Oxaamidination method of oxo-compound | |
CN1401640A (en) | Process for preparing epoxy cyclohexane by catalytic cyclooxidation of cyclohexene | |
CN1775360A (en) | Method for increasing ketone compound ammonia oxidation catalyst stability | |
CN104557450B (en) | A kind of method of oxidizing ethyle alkyl | |
CN1142147C (en) | Method for synthesizing hexanolactam by using titanium silicon molecular sieve to catalyze gas phase rearrangement of cyclohexanone-oxime | |
CN104415743B (en) | Regenerating method of titanium-containing catalyst | |
CN102294267A (en) | Preparation method and application of zinc oxide solid borne tetra (pentafiuorophenyl)ferriporphyrin | |
CN100337744C (en) | Catalyst system of hydrogen peroxide for redox cycloethane | |
CN1860087A (en) | Method for producing cumene and method for producing propylene oxide including the same method |
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 | ||
CX01 | Expiry of patent term |
Granted publication date: 20050727 |
|
CX01 | Expiry of patent term |