CN104107729A - Method for regenerating epoxidation catalyst - Google Patents
Method for regenerating epoxidation catalyst Download PDFInfo
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- CN104107729A CN104107729A CN201310129852.6A CN201310129852A CN104107729A CN 104107729 A CN104107729 A CN 104107729A CN 201310129852 A CN201310129852 A CN 201310129852A CN 104107729 A CN104107729 A CN 104107729A
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Abstract
The invention relates to a method for regenerating an epoxidation catalyst. The problems of product pollution, low efficiency and no long period running due to the low stability of a regenerated catalyst in the prior art are mainly solved. The method is characterized in that an organic solvent and a drying gas containing a silylating reagent are used to carry out in situ carbon dissolving and silylating treatment on an inactivated catalyst. The method well solves the problems, and can be used in the industrial production of olefin epoxidation catalyst regeneration.
Description
Technical field
The present invention relates to a kind of renovation process of epoxidation catalyst, wherein said catalyst is the SiO 2 catalyst of a class titaniferous.This catalyst is for the reaction system taking organic peroxide as oxidizer catalytic oxyalkylene hydrocarbons and their derivates production respective rings oxide.
Background technology
Taking organic peroxide as oxidant, on titaniferous SiO 2 catalyst, catalytic oxidation alkene is the main method of industrial production epoxides.For example, taking hydrogen peroxide ethylbenzene (EBHP) as oxidant, adopt titaniferous SiO 2 catalyst (as US3923843 and the disclosed catalyst Ti/SiO of US4367342
2) production expoxy propane; Or taking hydrogen phosphide cumene (CHP) or hydrogen peroxide ethylbenzene (EBHP) as oxidant, adopt the technology such as Ti-MCM41 Catalyst Production expoxy propane (as CN1500004A and the disclosed catalyst of CN1248579A).In these catalytic epoxidation systems, along with reaction is carried out, because partially catalyzed agent activated centre is covered by carbon containing byproduct of reaction, the activity of catalyst has decline to a certain degree.In the time that activity declines too lowly and can not meet normal need of production, will change fresh catalyst or to the decaying catalyst processing of regenerating.In industrial production, for reducing production costs, pay the utmost attention to decaying catalyst is regenerated.
Document WO9949972 discloses a kind of regeneration Ti/SiO
2the method of catalyst, the method will add the presoma of certain density active component titanium in reaction mass, the regeneration of catalyst and epoxidation reaction are carried out simultaneously.Although the method can make the activity of catalyst be maintained or recover, in product, the existence of titanium compound not only makes product be polluted, and has also increased the energy consumption that rectifying separates.
Calcination processing is typical catalyst regeneration technology, and document US5753576, US5741749, US6169050, US6380119 and US6790969 disclose this.Use when calcination processing, the material with carbon element of deposition at high temperature burns, or thermal decomposition removes, thereby makes catalyst regeneration.But said method makes deformation of catalyst particles owing at high temperature reacting, and is difficult to be applied to the reactor of multi-tubular reactor or jacketed reactor and so on.Therefore, people have furtherd investigate and use solvent clean processing to carry out the method for catalyst regeneration in recent years.
Document US5916835 discloses the method that makes decaying catalyst regeneration by using various solvents to carry out cleaning treatment.The method is used methyl alcohol to carry out solvent clean at 50 ~ 250 DEG C and processes 0.5 ~ 12 hour.But owing to need to using oxygen at 400 ~ 900 DEG C of additional steps of calcining, therefore said method runs into some problems, and whether the activity of the catalyst of regeneration can keep the long period not also to be confirmed.
In order to improve the efficiency of catalyst regeneration, shorten the recovery time, document US6066750 discloses a kind of method that makes catalyst regeneration.The method is included in 150 ~ 250 DEG C to adding ammonium or alkali metal cation in methyl alcohol and making catalyst regeneration.But if also leave metal ion in reactor after catalyst regeneration process, metal ion can become impurity, and the solvent using is difficult to reclaim.
Document US6063941 discloses a kind of catalyst recovery process, wherein can make catalyst effectively regenerate by the cleaning treatment comprising the following steps: at 50 ~ 100 DEG C, first use methyl alcohol, then using and being adjusted to pH value by NaOH is that the aqueous hydrogen peroxide solution of 4 ~ 72 ~ 5 % by weight cleans.But, in this patent, do not specifically describe the result of catalyst regeneration.
Document US6403514 discloses and has used the aqueous hydrogen peroxide solution that has added 30 % by weight of fluoridizing inorganic compound to carry out the method for catalyst regeneration.But, after catalyst regeneration, need to use air or oxygen to carry out calcining step at 400 ~ 600 DEG C, to remove deionization.In addition, although at least 80% original catalytic activity it is reported can recover, in this patent, not mention whether the activity of the catalyst of regeneration can keep the long period.
Document US5620935 discloses the method that uses aqueous hydrogen peroxide solution to make catalyst regeneration as oxidant, is wherein noted that it is very important for catalyst regeneration that reaction temperature is remained on to the temperature that approaches hydrogen peroxide boiling point.But for the effect of regeneration, this patent has only been mentioned the recovery of original catalytic activity, and do not confirm whether the activity of the catalyst of regeneration can keep the long period.
Document EP1489074 discloses the method that uses washed with methanol processing to make catalyst regeneration, being equivalent to reclaim the methyl alcohol that is used for catalyst regeneration after time of 2 ~ 30% of regenerative process required total time.Therefore, the catalyst of regeneration can keep active for a long time like this, keeps active more than 300 hours or 300 hours.But, only use the catalyst recovery process of this solvent only effective for the situation of part inactivation.In situation about sharply declining at most of inactivation or due to reactor problem catalyst activity, even if catalyst can be regenerated, its activity is also difficult to return to predetermined level or higher than predetermined level.
Document CN1501839A also discloses a kind of renovation process of titaniferous SiO 2 catalyst, and the method utilizes propylene or isopropylbenzene to wash decaying catalyst under uniform temperature and pressure, thereby the activity of catalyst is recovered to a certain extent.But, due in long-term epoxidization reaction process, except partially catalyzed agent activated centre is covered by byproduct of reaction, on the other hand, be subject to the impact of a small amount of water in reaction medium, the hydroxyl of catalyst surface increases, hydrophily strengthens, thereby cause hydrophobicity to weaken, the bad stability of catalyst, this is also a major reason that causes catalysqt deactivation.
Therefore, how fundamentally to solve the regeneration problem of decaying catalyst, and make the catalyst after regeneration there is high stability, become the important topic that silicon oxide catalyst containing titanium can be applied in epoxidation reaction of olefines.
Summary of the invention
Technical problem to be solved by this invention is product pollution in prior art, inefficiency, and the poor catalyst stability after regeneration can not ensure the problem of long-term operation, and a kind of renovation process of new epoxidation catalyst is provided.The method can directly be carried out in reactor, have efficient, without product pollution, catalyst activity after regeneration is high, the feature of good stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of renovation process of epoxidation catalyst, comprises the following steps:
A) make in epoxidation reaction of olefines to use and the epoxidation catalyst of inactivation contacts with carbon solution, obtain precursor I;
B) under normal pressure, use remaining carbon solution in inert gas purge precursor I, obtain precursor II;
C) make to contact with precursor II containing the dry gas of silylating reagent, obtain the epoxidation catalyst after regeneration.
Preferably, step a) temperature is 100 ~ 300 DEG C, and pressure is 0.1 ~ 10MPa, and air speed is 0.01 ~ 10 hour
-1.
More preferably, step a) temperature is 120 ~ 250 DEG C, and pressure is 0.1 ~ 5MPa; Air speed is 0.1 ~ 5 hour
-1.
Preferably, step b) purges the boiling point of temperature higher than carbon solution.
More preferably, step b) purges temperature higher than 5 ~ 50 DEG C of the boiling points of carbon solution.
Preferably, step c) temperature is 10 ~ 500 DEG C, and pressure is 0.1 ~ 10MPa, and the volume content of silylating reagent in inertia dry gas is 0.5 ~ 90%.
More preferably, step c) temperature is 25 ~ 350 DEG C, and pressure is 0.1 ~ 5MPa, and the volume content of silylating reagent in inertia dry gas is 1 ~ 60%.
Preferably, described epoxidation catalyst is selected from the amorphous silica catalyst Ti/SiO of Ti-HMS, Ti-MCM41 or titaniferous
2.
Preferably described carbon solution is selected from least one in benzene,toluene,xylene, ethylbenzene, diethylbenzene, n-proplbenzene, isopropylbenzene, propane, butane, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, hendecane, dodecane, ethene, propylene, butylene, butadiene, amylene, cyclopentene, hexene, cyclohexene or heptene.
More preferably, when described carbon solution is selected from epoxidation reaction, oxidant is dissolved in solvent wherein, or the alkene using when epoxidation reaction.
Most preferably, in the time adopting hydrogen peroxide ethylbenzene to make oxidant, carbon solution is ethylbenzene; In the time adopting hydrogen phosphide cumene to make oxidant, carbon solution is isopropylbenzene; In the time adopting TBHP to make oxidant, carbon solution is the tert-butyl alcohol; In the time adopting cyclohexyl hydroperoxide to make oxidant, carbon solution is cyclohexane; In the time that reaction is ethylene epoxidizing, carbon solution is ethene; In the time that reaction is epoxidation of propylene, carbon solution is propylene; In the time that reaction is butene-1 epoxidation, carbon solution is butene-1; In the time that reaction is epoxidation of cyclohexene, carbon solution is that cyclohexene carries out molten carbon.
Preferably, described in step b), inert gas is selected from nitrogen, helium, neon, argon gas, carbon monoxide, carbon dioxide or methane.
Preferably, dry gas comprises dry air, nitrogen, hydrogen, helium, neon, argon gas, carbon monoxide or methane described in step c), and its dew point is-20 ~-70 DEG C.
Preferably, described silylating reagent is selected from least one in organosilan, organosilazanes or Organosilyl amine.Wherein, described organosilan is selected from least one in trim,ethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, dimethyldichlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane.Described organosilazanes is selected from HMDS, 1,1,3,3-tetramethyl-disilazane, 1,3-bis-(chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1, at least one in 3,3-tetramethyl-disilazane or 1,3-diphenyl tetramethyl-disilazane.Described Organosilyl amine is selected from least one in N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silicyl imidazoles, N-dimethyl isopropyl silicyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide;
More preferably, described silylating reagent is selected from trim,ethylchlorosilane, chlorotriethyl silane, dimethyldichlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, HMDS, 1,1, at least one in 3,3-tetramethyl-disilazane, N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
Most preferably, described silylating reagent is selected from least one in trim,ethylchlorosilane, dimethyldichlorosilane, HMDS or 1,1,3,3-tetramethyl-disilazane.
In technique scheme, the catalyst of regenerating refers to the inactivation solid catalyst of producing epoxides taking organic peroxide as oxidizer catalytic oxyalkylene.Epoxidation reaction both can be carried out in slurry bed reactor, also can in fixed bed, carry out, but from the reality of large-scale industrial production, preferentially adopt fixed bed reactors.Catalyst wherein can be according to the needs of reaction process condition, are prepared into the various appearance forrns such as powdery, spherical, granular, strip, sheet, three weeds shapes.
As olefin epoxidation catalysts, the preferential silica solid catalyst that adopts titaniferous, wherein titanium is to adopt direct or rear synthetic technology, sol gel reaction or coprecipitation reaction by titanium dioxide predecessor and silica predecessor make, or are interacted and formed by the silicon hydroxyl of titanium precursor thing and silica surface.Can comprise the Ti-HMS catalyst with hexagonal mesoporous structure, Ti-MCM41 catalyst and the Ti/SiO prepared by sol-gel process, coprecipitation or chemical deposition as the example of this titaniferous SiO 2 catalyst
2(unformed) catalyst.
The alkene that can carry out epoxidation reaction on catalyst of the present invention comprises the olefin and its derivatives containing 2-40 carbon atom such as ethene, propylene, 1-butylene, 2-butylene, butadiene, amylene, cyclohexene, styrene, ENB.The oxidant adopting comprises the organic peroxides such as hydrogen peroxide ethylbenzene, hydrogen phosphide cumene, TBHP and cyclohexyl hydroperoxide.
Epoxidation reaction is carried out under liquid-phase condition in solvent, and under reaction temperature and pressure, the solvent adopting must be in a liquid state, and reactant and product are to inertia.Selected solvent can comprise the various aromatic hydrocarbons being in a liquid state under reaction temperature and pressure, alkane, cycloalkane, alcohol and derivative thereof.Preferably adopt organic peroxide to be dissolved in solvent wherein, as the isopropylbenzene in the ethylbenzene in hydrogen peroxide ethylbenzene solution, hydrogen phosphide cumene solution etc.In this case, without adding again other solvent, can make solvent with ethylbenzene and isopropylbenzene respectively.In addition, also can adopt the alkene of excessive participation reaction to make solvent.
During catalytic epoxidation, reaction can maintain under a certain specified temp to be carried out, and also can, according to response situation, for keeping higher conversion ratio, and progressively improve reaction temperature.In general, reaction temperature is 25 ~ 200 DEG C, and temperature is too low, reaction cannot carry out or conversion ratio too low, excess Temperature causes the decomposition of organic peroxide.Reaction pressure is generally 0.1 ~ 10MPa, and in reaction, the mol ratio of alkene/organic peroxide is 1 ~ 20.
Described catalyst recovery process directly in reactor original position carry out.Regeneration wherein both can take dynamic mode to operate, and also can adopt static mode to carry out.
The carbon solution adopting when regeneration comprises: benzene and the homologues thereof such as benzene,toluene,xylene, ethylbenzene, diethylbenzene, n-proplbenzene and isopropylbenzene; Alkane and the cycloalkane such as propane, butane, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, hendecane and dodecane; Alkene and the cycloolefins such as ethene, propylene, butylene, butadiene, amylene, cyclopentene, hexene, cyclohexene and heptene.When preferred epoxidation reaction, oxidant is dissolved in solvent wherein.As, in the time adopting hydrogen peroxide ethylbenzene to make oxidant, preferably ethylbenzene is made carbon solution; In the time adopting hydrogen phosphide cumene to make oxidant, preferably isopropylbenzene is made carbon solution; In the time adopting TBHP to make oxidant, preferred tertiary butanols is made carbon solution; In the time adopting cyclohexyl hydroperoxide to make oxidant, preferably cyclohexane give carbon solution.In addition, the alkene using when carbon solution also preferably participates in epoxidation reaction.As, in the time that reaction is ethylene epoxidizing, adopt the molten carbon of ethene; In the time that reaction is epoxidation of propylene, adopt the molten carbon of propylene; In the time that reaction is butene-1 epoxidation, adopt the molten carbon of butene-1; In the time that reaction is epoxidation of cyclohexene, adopt cyclohexene to carry out molten carbon; Etc., the like.Temperature when molten carbon is preferably high 10 ~ 50 DEG C than epoxidation reaction temperature, and pressure is 0.1 ~ 5.0MPa preferably, to ensure that molten carbon carries out under full liquid-phase condition.Molten carbon is complete, and purging when carbon solution, the inert gas adopting comprises that nitrogen, helium, neon, argon gas, carbon monoxide, carbon dioxide, methane etc. are the gas of inertia under purging condition, and temperature is preferably higher than 5 ~ 50 DEG C of the boiling points of carbon solution.
The silica solid catalyst of olefin epoxidation catalysts, particularly titaniferous, in long-term operation process, on the one hand, the activated centre of catalyst is covered gradually by larger molecule accessory substance, activity decreased; On the other hand, catalyst surface hydrophobicity weakens, elective reduction.Therefore, adopt the inventive method, decaying catalyst is being carried out after molten carbon processing, then silanization grafting processing is carried out in its surface.In the time that silanization is processed, the silicon alkyl radical reaction in silicon hydroxyl and the silylating reagent of silica surface, the silica-based carrier surface that is grafted to of alkyl, makes catalyst have hydrophobic property.Like this in epoxidization reaction process, micro-moisture in raw material just can not adsorb at catalyst surface, thereby strengthen the stability of catalyst active center, avoid object product expoxy propane to react with water generation hydrolysis simultaneously, reduce selectivity of product, and can avoid to a great extent covering activated centre compared with macromolecular generation with in catalyst surface absorption, affect activity and the stability of catalyst, can significantly improve the performance of regenerated catalyst.Adopt catalyst recovery process of the present invention, regenerated catalyst efficiently, and can not produce pollution to product, catalyst activity after regeneration can return to the level that approaches fresh catalyst, and good stability, can reach 600 hours, has obtained good technique effect.
Detailed description of the invention
[embodiment 1]
In stainless steel fixed bed reactors, add 5.0g Ti-HMS beaded catalyst (20-40 order), propylene and 40.0wt% hydrogen phosphide cumene CHP(are dissolved in isopropylbenzene) after mixing, react by beds.Wherein C
3h
6/ CHP=7.0(mol ratio), WHSV (CHP)=6.0 hour
-1, pressure=3.0MPa, control reaction temperature be 100 DEG C.When reaction proceeded to after 1200 hours, stop material supply, pass into isopropylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 150 DEG C and 0.5MPa, after washing catalyst detects without CHP to reactor outlet, under similarity condition, continue the molten carbon of logical isopropylbenzene and process 24 hours.Reduction system pressure is normal pressure, and rising temperature to 200 DEG C passes into nitrogen in beds, dries up catalyst.Regulate bed temperature to 180 DEG C, normal pressure, it is 10.0% drying nitrogen 6 hours that circulation passes into HMDS volume content.Under this temperature and pressure, switch to nitrogen blowing to reactor outlet and detect without HMDS, complete the regeneration of catalyst, regeneration result is as shown in table 1 and table 3.
[embodiment 2]
Reaction condition is with [embodiment 1].When reaction proceeded to after 1200 hours, stop material supply, pass into isopropylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 150 DEG C and 0.5MPa, after washing catalyst detects without CHP to reactor outlet, under similarity condition, continue the molten carbon of logical isopropylbenzene and process 24 hours.Reduction system pressure is normal pressure, and rising temperature to 200 DEG C passes into nitrogen in beds, dries up catalyst.In beds, pass into nitrogen, reduction system pressure is normal pressure, and rising temperature to 200 DEG C, dries up beds.Regulate bed temperature to 250 DEG C, normal pressure, it is 12.0% drying nitrogen 6 hours that circulation passes into trim,ethylchlorosilane volume content.Under this temperature and pressure, switch to nitrogen blowing to reactor outlet and detect without trim,ethylchlorosilane, complete the regeneration of catalyst, regeneration result is as shown in table 1 and table 3.
[embodiment 3]
Reaction condition is with [embodiment 1].When reaction proceeded to after 1200 hours, stop material supply, pass into isopropylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 150 DEG C and 0.5MPa, after washing catalyst detects without CHP to reactor outlet.Rising temperature to 180 DEG C, pressure is increased to 1.5MPa, and static molten carbon is processed 48 hours.Reduction system pressure is normal pressure, and rising temperature to 200 DEG C passes into nitrogen in beds, dries up catalyst.In beds, pass into nitrogen, reduction system pressure is normal pressure, and rising temperature to 200 DEG C, dries up beds.Regulate bed temperature to 250 DEG C, normal pressure, it is 12.0% drying nitrogen 6 hours that circulation passes into HMDS volume content.Under this temperature and pressure, switch to nitrogen blowing to reactor outlet and detect without HMDS, complete the regeneration of catalyst, regeneration result is as shown in table 1 and table 3.
[embodiment 4]
Reaction condition is with [embodiment 1].When reaction proceeded to after 1200 hours, stop material supply, pass into propylene, air speed 2.0 hours
-1, regulate temperature and pressure to be respectively 135 DEG C and 4.0MPa, after washing catalyst detects without CHP to reactor outlet, under similarity condition, continue the molten carbon of logical propylene and process 24 hours.Reduction system pressure is normal pressure, and 100 DEG C of temperature pass into nitrogen in beds, dry up catalyst.Regulate bed temperature to 250 DEG C, normal pressure, it is 12.0% drying nitrogen 6 hours that circulation passes into trim,ethylchlorosilane volume content.Under this temperature and pressure, switch to nitrogen blowing to reactor outlet and detect without trim,ethylchlorosilane, complete the regeneration of catalyst, regeneration result is as shown in table 1 and table 3.
[embodiment 5]
In stainless steel fixed bed reactors, add 5.0g Ti-HMS beaded catalyst (20-40 order), propylene and 18.0wt% hydrogen peroxide ethylbenzene EBHP (being dissolved in ethylbenzene) react by beds after mixing.Wherein propylene/EBHP=12(mol ratio), WHSV (CHP)=5.0 hour
-1, pressure=3.1MPa, control reaction temperature be 102 DEG C.When reaction proceeded to after 1200 hours, stop material supply, pass into ethylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 140 DEG C and 0.8MPa, after washing catalyst detects without EBHP to reactor outlet, under similarity condition, continue the molten carbon of logical ethylbenzene and process 24 hours.Reduction system pressure is normal pressure, and rising temperature to 200 DEG C passes into nitrogen in beds, dries up catalyst.Regulate bed temperature to 180 DEG C, normal pressure, it is 10.0% drying nitrogen 6 hours that circulation passes into HMDS volume content.Under this temperature and pressure, switch to nitrogen blowing to reactor outlet and detect without HMDS, complete the regeneration of catalyst, regeneration result is as shown in table 2 and table 4.
[comparative example 1]
Reaction condition is with [embodiment 1].When reaction proceeded to after 1200 hours, stop material supply, pass into isopropylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 150 DEG C and 0.5MPa, after washing catalyst detects without CHP to reactor outlet, under similarity condition, continue the molten carbon of logical isopropylbenzene and process 24 hours.The Evaluation results that rear catalyst is washed in molten carbon processing is as shown in table 1 and table 3.
[comparative example 2]
Reaction condition is with [embodiment 5].When reaction proceeded to after 1200 hours, stop material supply, pass into ethylbenzene, air speed 4.0 hours
-1, regulate temperature and pressure to be respectively 140 DEG C and 0.8MPa, after washing catalyst detects without EBHP to reactor outlet, under similarity condition, continue the molten carbon of logical ethylbenzene and process 24 hours.Molten carbon is processed the Evaluation results of rear catalyst as shown in table 2 and table 4.
Table 1 catalyst regeneration result
Note: CHP-hydrogen phosphide cumene, PO-expoxy propane, PO is selective-and expoxy propane is selective to CHP's.
Reaction condition after regeneration is with before regenerating.
Table 2 catalyst regeneration result
Note: EBHP-hydrogen peroxide ethylbenzene, PO-expoxy propane, PO is selective-and expoxy propane is selective to EBHP's.
Reaction condition after regeneration is with before regenerating.
The stability experiment of table 3 regenerated catalyst
The stability experiment of table 4 regenerated catalyst
Claims (10)
1. a renovation process for epoxidation catalyst, comprises the following steps:
A) make in epoxidation reaction of olefines to use and the epoxidation catalyst of inactivation contacts with carbon solution, obtain precursor I;
B) under normal pressure, use remaining carbon solution in inert gas purge precursor I, obtain precursor II;
C) make to contact with precursor II containing the dry gas of silylating reagent, obtain the epoxidation catalyst after regeneration.
2. the renovation process of epoxidation catalyst according to claim 1, is characterized in that step a) temperature is 100 ~ 300 DEG C, is preferably 120 ~ 250 DEG C; Pressure is 0.1 ~ 10MPa, is preferably 0.1 ~ 5MPa; Air speed is 0.01 ~ 10 hour
-1, be preferably 0.1 ~ 5 hour
-1.
3. the renovation process of epoxidation catalyst according to claim 1, is characterized in that step b) purges the boiling point of temperature higher than carbon solution, preferably higher than 5 ~ 50 DEG C of the boiling points of carbon solution.
4. the renovation process of epoxidation catalyst according to claim 1, is characterized in that step c) temperature is 10 ~ 500 DEG C, is preferably 25 ~ 350 DEG C; Pressure is 0.1 ~ 10MPa, is preferably 0.1 ~ 5MPa; The volume content of silylating reagent in inertia dry gas is 0.5 ~ 90%, is preferably 1 ~ 60%.
5. the renovation process of epoxidation catalyst according to claim 1, is characterized in that described epoxidation catalyst is selected from the amorphous silica catalyst Ti/SiO of Ti-HMS, Ti-MCM41 or titaniferous
2.
6. the renovation process of epoxidation catalyst according to claim 1, is characterized in that described carbon solution is selected from least one in benzene,toluene,xylene, ethylbenzene, diethylbenzene, n-proplbenzene, isopropylbenzene, propane, butane, pentane, hexane, cyclohexane, heptane, octane, nonane, decane, hendecane, dodecane, ethene, propylene, butylene, butadiene, amylene, cyclopentene, hexene, cyclohexene or heptene; Preferably oxidant is dissolved in solvent wherein when epoxidation reaction, or the alkene using when epoxidation reaction.
7. the renovation process of epoxidation catalyst according to claim 6, is characterized in that carbon solution is ethylbenzene in the time adopting hydrogen peroxide ethylbenzene to make oxidant; In the time adopting hydrogen phosphide cumene to make oxidant, carbon solution is isopropylbenzene; In the time adopting TBHP to make oxidant, carbon solution is the tert-butyl alcohol; In the time adopting cyclohexyl hydroperoxide to make oxidant, carbon solution is cyclohexane;
In the time that reaction is ethylene epoxidizing, carbon solution is ethene; In the time that reaction is epoxidation of propylene, carbon solution is propylene; In the time that reaction is butene-1 epoxidation, carbon solution is butene-1; In the time that reaction is epoxidation of cyclohexene, carbon solution is that cyclohexene carries out molten carbon.
8. the renovation process of epoxidation catalyst according to claim 1, is characterized in that described in step b) that inert gas is selected from nitrogen, helium, neon, argon gas, carbon monoxide, carbon dioxide or methane; Described in step c), dry gas comprises dry air, nitrogen, hydrogen, helium, neon, argon gas, carbon monoxide or methane, and its dew point is-20 ~-70 DEG C.
9. the renovation process of epoxidation catalyst according to claim 1, is characterized in that described silylating reagent is selected from least one in organosilan, organosilazanes or Organosilyl amine.
10. the renovation process of epoxidation catalyst according to claim 9, is characterized in that described organosilan is selected from least one in trim,ethylchlorosilane, chlorotriethyl silane, tripropyl chlorosilane, tributyl chlorosilane, dimethyldichlorosilane, 3,5-dimethylphenyl chlorosilane, dimethyl ethyl chlorosilane, dimethyl n propyl chloride silane, dimethyl isopropyl chloride silane, normal-butyl dimethylchlorosilane or aminomethyl phenyl chlorosilane; Preferably at least one in trim,ethylchlorosilane, chlorotriethyl silane, dimethyldichlorosilane, 3,5-dimethylphenyl chlorosilane or dimethyl ethyl chlorosilane; More preferably at least one in trim,ethylchlorosilane or dimethyldichlorosilane;
Described organosilazanes is selected from HMDS, 1,1,3,3-tetramethyl-disilazane, 1,3-bis-(chloromethyl) tetramethyl-disilazane, 1,3-divinyl-1,1, at least one in 3,3-tetramethyl-disilazane or 1,3-diphenyl tetramethyl-disilazane; Preferably at least one in HMDS or 1,1,3,3-tetramethyl-disilazane; More preferably at least one in HMDS or 1,1,3,3-tetramethyl-disilazane;
Described Organosilyl amine is selected from least one in N-trimethyl-silyl-imidazole, N-t-butyldimethylsilyl imidazoles, N-dimethylethylsilyl imidazoles, N-dimethyl n propyl group silicyl imidazoles, N-dimethyl isopropyl silicyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide; Preferably at least one in N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-trimethyl silyl dimethyl amine or N-trimethyl silyl diethylamide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144647A (en) * | 2018-01-16 | 2018-06-12 | 河南能源化工集团研究院有限公司 | High stability copper-based catalysts of preparing ethylene glycol by using dimethyl oxalate plus hydrogen and preparation method thereof |
| CN109092283A (en) * | 2018-08-22 | 2018-12-28 | 万华化学集团股份有限公司 | A kind of regeneration method of olefin epoxidation catalysts and application thereof |
| CN110653009A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Method for on-line activity recovery of heavy oil hydrotreating catalyst and agent unloading method |
| CN110655947A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN112619712A (en) * | 2020-12-17 | 2021-04-09 | 红宝丽集团股份有限公司 | Regeneration method of deactivated epoxidation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513109A (en) * | 2011-12-16 | 2012-06-27 | 武汉大学 | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof |
| CN102626649A (en) * | 2012-03-21 | 2012-08-08 | 重庆大学 | Oxygen reduction non-noble metal catalyst and preparation method thereof |
-
2013
- 2013-04-16 CN CN201310129852.6A patent/CN104107729B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513109A (en) * | 2011-12-16 | 2012-06-27 | 武汉大学 | Double-functional catalyst of carbon-based non-noble-metal oxygen electrode and preparation method thereof |
| CN102626649A (en) * | 2012-03-21 | 2012-08-08 | 重庆大学 | Oxygen reduction non-noble metal catalyst and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144647A (en) * | 2018-01-16 | 2018-06-12 | 河南能源化工集团研究院有限公司 | High stability copper-based catalysts of preparing ethylene glycol by using dimethyl oxalate plus hydrogen and preparation method thereof |
| CN110653009A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Method for on-line activity recovery of heavy oil hydrotreating catalyst and agent unloading method |
| CN110655947A (en) * | 2018-06-30 | 2020-01-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating method |
| CN109092283A (en) * | 2018-08-22 | 2018-12-28 | 万华化学集团股份有限公司 | A kind of regeneration method of olefin epoxidation catalysts and application thereof |
| CN109092283B (en) * | 2018-08-22 | 2021-04-20 | 万华化学集团股份有限公司 | Regeneration method and application of olefin epoxidation catalyst |
| CN112619712A (en) * | 2020-12-17 | 2021-04-09 | 红宝丽集团股份有限公司 | Regeneration method of deactivated epoxidation catalyst |
| CN112619712B (en) * | 2020-12-17 | 2023-12-05 | 红宝丽集团股份有限公司 | Regeneration method of deactivated epoxidation catalyst |
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