CN103182321A - Treatment method of deactivated titanium-silicon molecular sieve - Google Patents
Treatment method of deactivated titanium-silicon molecular sieve Download PDFInfo
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- CN103182321A CN103182321A CN2011104492660A CN201110449266A CN103182321A CN 103182321 A CN103182321 A CN 103182321A CN 2011104492660 A CN2011104492660 A CN 2011104492660A CN 201110449266 A CN201110449266 A CN 201110449266A CN 103182321 A CN103182321 A CN 103182321A
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Abstract
The invention relates to a treatment method of a deactivated titanium-silicon molecular sieve. The method includes: mixing a reclaimed rubber with a filtrated stock obtained in a titanium silicon molecular sieve synthesis process to obtain a mixed solution, then contacting the mixed solution with a deactivated titanium-silicon molecular sieve and placing them in a sealed reaction kettle, conducting a treatment for at least 2h at a temperature of 120-200DEG C, and then drying and roasting the product under normal temperature and pressure to obtain a regenerated titanium silicon molecular sieve. Specifically, the reclaimed rubber contains a silicon source, a titanium source and organic alkali, the reaction kettle contains a water amount able to form saturated steam under the reaction conditions, and the weight ratio of the water to the deactivated titanium-silicon molecular sieve is less than 1.2. Meanwhile, the treating amount of the deactivated titanium-silicon molecular sieve is at least 10g/L reaction kettle volume. After treatment by the method, the titanium-silicon molecular sieve has equal activity to a fresh agent. The regeneration process has low material consumption and high yield, and is green and efficient.
Description
Technical field
The present invention relates to a kind of method of handling deactivated titanium silicon molecular sieve.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The TS-1 that the MFI structure is arranged that has synthesized at present, the TS-2 of MEL structure, and have than the Ti-MWW of macroporous structure etc.This molecular sieve analog is to many organic oxidizing reactions, for example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylating, cyclohexanone oximate, alcohol have good selective oxidation performance and advantages of high catalytic activity, and they have a good application prospect as the oxidation-reduction type molecular sieve catalyst.
TS-1 introduces formed a kind of new titanium-silicone molecular sieve with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve with ZSM-5 structure with the transition metal titanium, not only have the catalysed oxidn of titanium, but also have the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Because inactivation TS-1 molecular sieve is in organic oxidation reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, oxidizing process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, the economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity, therefore have great prospects for commercial application.People such as Taramasso disclose the preparation method (US4410501) of TS-1 molecular sieve first, this method is to prepare a kind of reactant mixture that contains silicon source, titanium source, organic base and/or basic anhydride earlier, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.
HTS is as catalyst, after in organic oxidation reaction, moving a period of time, impurity, accessory substance are assembled the obstruction duct in micropore, the framework silicon titanium species changes into non-skeleton species, activated centre loss owing to introduced under reaction condition, skeleton caves in etc., cause the catalytic performance variation, deactivation phenomenom occurs.
For the HTS of inactivation in the organic oxidation reaction, its conventional regeneration method mainly concentrates on several common methods such as roasting, solvent wash and oxidant oxidation.For example, the employing molecular sieve containing titanium epoxidation of propylene of EP0100119 is to prepare the method for expoxy propane, and wherein the regeneration of Ti Chuing has 550 ℃ of high-temperature roastings, and the solvent wash of methyl alcohol or course of reaction use; US5620935 discloses a kind of method that adopts the aqueous hydrogen peroxide solution regenerated from washing, and preferred wash temperature is more than 100 ℃; US6878836B2 discloses a kind of method that adopts the regeneration of methyl alcohol high-temperature wash, and this method is with the wash temperature more than 100 ℃ decaying catalyst to be carried out methanol wash; CN1461671A discloses a kind of renovation process of titanium-containing catalyst, is to handle with hydrogenperoxide steam generator under the condition that the mineral acid thing exists; CN101480623A discloses the renovation process of methyl alcohol dissolving washing, hydrogen peroxide oxidation and steam blowing; CN101439299A discloses a kind of renovation process with organic acid and hydrogen peroxide.CN101602011A discloses a kind of renovation process of Ti-MWW HTS usefulness bronsted lowry acids and bases bronsted lowry solution-treated of inactivation.But this method operating process very complicated filters repeatedly, washs and produces a large amount of industrial wastewaters such as acid, ammonia nitrogen that contain, material consumption and energy consumption height, and environmental protection and economy are restricted.
In the technology of existing preparation HTS (as USP4410501, and Zeolites, 1992, Vol.12:943) in, the utilization rate in silicon source is about 75～95%, and organic base template agent utilization rate is about 20～95%, the template agent of 5～25% silicon and 5～80% of having an appointment like this is retained in and does not obtain in the synthesis mother liquid utilizing, if directly discharge as sewage, not only cause very big waste, and can pollute environment.Propose utilization among CN1089279C and the CN101134575B and synthesize the method that the waste liquid of TS-1 zeolite synthesizes the TS-1 zeolite.But do not see and utilize this filtration waste liquid to handle the report of deactivated titanium silicon molecular sieve.
Summary of the invention
The a large amount of experiment basis how the present inventor regenerates at the HTS of research inactivation are surprised to find that, when mixing, the filtrated stock that a kind of reclaimed rubber and HTS building-up process are obtained obtains mixed liquor, again with this mixed liquor hydrothermal treatment consists during because of the HTS of reason inactivations such as run off in the activated centre, skeleton caves in, after product drying, the roasting, has good especially regeneration effect, HTS activity after the processing can return to fresh dose level, the regenerative process material consumption is low, the yield height.This method can also be saved cost, significantly reduces waste liquid to the pollution of environment.More surprisingly, this its relative crystallinity of method gained sample also is restored, and illustrates to adopt the method regeneration back framework of molecular sieve integrity degree to obtain repairing and keeping.Based on this, finish the present invention.
The method of processing deactivated titanium silicon molecular sieve provided by the present invention, the filtrated stock that a kind of reclaimed rubber and HTS building-up process are obtained mixes and obtains mixed liquor, again described mixed liquor is contacted and places under the closed reactor hydrothermal condition with the HTS of inactivation and handle, then at normal temperatures and pressures with the product drying, the HTS that roasting obtains regenerating, wherein, described reclaimed rubber contains the silicon source, the titanium source, organic base, contain in the described closed reactor under reaction condition form saturated steam and with the weight ratio of the HTS of inactivation less than 1.2 the water yield, the treating capacity of the HTS of inactivation is 10g/L reactor volume at least.
The method of processing deactivated titanium silicon molecular sieve provided by the invention is the method for the regeneration of deactivated HTS of a kind solid phase, has following advantage:
Part material when 1, utilizing HTS synthetic " waste liquid " as regeneration has not only been saved raw material, can also make refuse obtain utilizing, and has further reduced in the HTS building-up process pollution to environment.
2, deactivated molecular sieve is handled under the aqueous vapor condition with silicon, titanium and organic base material, repair framework of molecular sieve preferably, the mediation duct, remedy or the activated centre of repairing activity partial loss, its activity can maintain an equal level with fresh dose of activity, the silicon of Yin Ruing, titanium can be converted into the part of molecular sieve simultaneously, and the reconstituted product yield is higher.
3, HTS need not after filtration and washing procedure after regenerating, and directly drying, calcination process get final product, and supplies consumption reduces, and the three wastes are few, utilize commercial Application.
4, its relative crystallinity of the inventive method gained sample also is restored.
The specific embodiment
The method of processing deactivated titanium silicon molecular sieve provided by the invention, the filtrated stock that a kind of reclaimed rubber and HTS building-up process are obtained mixes and obtains mixed liquor, again described mixed liquor is contacted and places under the closed reactor hydrothermal condition with the HTS of inactivation and handle, then at normal temperatures and pressures with the product drying, the HTS that roasting obtains regenerating, wherein, described reclaimed rubber contains the silicon source, the titanium source, organic base, contain in the described closed reactor under reaction condition form saturated steam and with the weight ratio of the HTS of inactivation less than 1.2 the water yield, the treating capacity of the HTS of inactivation is 10g/L reactor volume at least.
HTS is as catalyst, after in the oxidation of organic oxidation reaction such as alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating, alcohol or alkane oxidation reaction (for example phenol hydroxylation, cyclohexanone oxamidinating, epoxidation of propylene), moving a period of time, because accessory substance is assembled the obstruction duct in micropore under reaction condition, the framework silicon titanium species changes into non-skeleton species, activated centre loss, skeleton caves in etc., cause the catalytic performance variation, deactivation phenomenom occurs.For example, in the phenol hydroxylation reaction, be catalyst with fresh TS-1 molecular sieve, the mol ratio of phenol and hydrogen peroxide is under 3: 1 the condition, carry out the phenol hydroxylation reaction, catalyst descends (dropping to below 12% from 25%) without phenol conversion after the recycling utilization five times, namely produces deactivation phenomenom.
In the method provided by the invention, described deactivated titanium silicon molecular sieve is the HTS of various inactivations, comprise TS-1, TS-2, Ti-Beta, Ti-MWW molecular sieve of inactivation etc., in an embodiment of the present invention, the regenerative process of the TS-1 molecular sieve of inactivation is compared detailed explanation.Method provided by the invention, can the HTS of deactivation phenomenom for example appear for the treatment of oxidation or the alkane oxidation reaction of alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating, alcohol after a period of time running in phenol hydroxylation, cyclohexanone oxamidinating, the epoxidation of propylene.This method is adapted to handle the undesirable situation of means effect in prior art especially, in the time of but can not making catalyst activity return to acceptable level as handling through regeneration such as roasting, solvent wash, adopt method provided by the invention can obtain satisfied regeneration effect.
In the method provided by the invention, the organic base described in the reclaimed rubber can be selected from and be organo-alkali compounds such as quaternary ammonium base compound, amine compound and alcohol amine compound.Described quaternary ammonium base compound can be selected from TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH etc., described amine compound can be ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine or hexamethylene diamine etc., and described alcohol amine compound can be MEA, diethanol amine or triethanolamine.The example of described organic base can for but be not limited to one or more mixture in TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine, the triethanolamine.The example of the mixture of described multiple organic base can for but be not limited to as the mixture of tetraethyl ammonium hydroxide and n-butylamine, the mixture of tetraethyl ammonium hydroxide and n-butylamine, the mixture of ethylenediamine and TPAOH, the mixture of di-n-propylamine and TPAOH, the mixture of tetraethyl ammonium hydroxide and TPAOH, the mixture of hexamethylene diamine and TPAOH.
In the method provided by the invention, the silicon source described in the reclaimed rubber can be the organosilicon source, also can be the inorganic silicon source, and the inorganic silicon source comprises silica, amorphous silica gel and Z type silica gel etc., and organosilicon source preferred formula is R
1 4SiO
4The organosilicon acid esters, R
1Be selected from the alkyl with 1～4 carbon atom, preferred R
1Be ethyl.
In the method provided by the invention, the titanium source described in the reclaimed rubber can be inorganic ti sources, can be the organic titanium source also, and inorganic ti sources comprises TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Deng, organic titanium source preferred formula is Ti (OR
2)
4Be organic titanate, wherein R
2The alkyl that preferably has 2～4 carbon atoms.
In the method provided by the invention, described reclaimed rubber refers to that hydrolysis under the condition that organic base exists forms by silicon source and titanium source.The mole of described reclaimed rubber consists of the silicon source: titanium source: organic base=(0.1～1): (0～0.1): (0.01～5), preferred 1: (0.01～0.05): (0.3～3), the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, organic base is with NH
3Meter.In hydrolytic process, control silicon is (with SiO
2Meter) with the molar ratio 1 of water: (1.5～100), be preferably 1: (20～50).
Satisfy the water yield forming under the reaction condition saturated steam and with the weight ratio of the HTS of inactivation less than 1.2 and the treating capacity of the HTS of the inactivation prerequisite for 10g/L reactor volume at least under, the weight ratio of the filtrated stock that described reclaimed rubber and described HTS building-up process obtain can be 100: (1～50000), the HTS of described inactivation and the weight ratio of described mixed liquor are 100: (10～120).
In the method provided by the invention, described filtration waste liquid refers to synthesis mother liquid, be after HTS utilizes traditional water process for thermosynthesizing crystallization synthetic, product is carried out remaining liquid after Separation of Solid and Liquid goes out HTS, because the general mode of filtering that adopts is separated, filter waste liquid or filter stoste so be also referred to as.This liquid contains soluble silicon species, titanium species and alkaline template agent, and there is certain difference in concentration according to different synthesis conditions, is well known to those skilled in the art.The composition of said filtrated stock includes but not limited to: the soluble silicon species are (with SiO
2Meter) mass content＜10%, the soluble titanium species are (with TiO
2Meter) mass content＜1%, alkaline template agent is (with NH
3Meter) mass content＜15%.In the specific embodiment of the present invention, preferably adopt the synthetic synthesis mother liquid of TS-1 molecular sieve.
In the method provided by the invention, described deactivated titanium silicon molecular sieve is with before reclaimed rubber mixes, through or can without roasting, preferably pass through roasting, the mass ratio of reclaimed rubber and filtrated stock is preferably 100: (10～500), the weight ratio of deactivated titanium silicon molecular sieve and mixed liquor (mixed liquor of reclaimed rubber and filtrated stock) more preferably 100: (30～100).
In the method provided by the invention, contain in the reactor under reaction condition form saturated steam and with the weight ratio of deactivated titanium silicon molecular sieve less than 1.2 the water yield, the water yield of described formation saturated steam can be provided by reaction kettle for reaction thing material, also can realize through adding outside steam.
In the method provided by the invention, treatment conditions are for carrying out 2～144h under 120～200 ℃, and preferred treatment conditions are for carrying out 6～72h under 135～180 ℃.
In the method provided by the invention, regeneration back HTS need not after filtration and washing procedure, and directly drying, calcination process get final product.Process dry and roasting is familiar with by those skilled in the art, and at this and have no special requirements, described drying can be carried out under the temperature between room temperature～200 ℃, and described roasting can be carried out 2～12h in air atmosphere between 300 ℃～800 ℃.
The invention will be further described below by embodiment, but therefore do not limit content of the present invention.
Among Comparative Examples and the embodiment, agents useful for same is commercially available chemically pure reagent.
The relative crystallinity R of sample
CAt first be X-ray diffraction (XRD) mensuration of carrying out sample at Siemens D5005 type x-ray diffractometer, radiographic source is CuK α
Being that the ratio of diffracted intensity (peak height) sum at the five fingers diffractive features peak between 22.5 °～25.0 ° is represented sample with respect to the degree of crystallinity of authentic specimen with sample and authentic specimen at 2 θ then, is authentic specimen with Comparative Examples 1 sample here.The relative crystallinity R of each sample
CData see Table 1.
Comparative Examples 1
This Comparative Examples is designated as X-1 for the method according to document US P4410501 record prepares the TS-1 sample.The filtration waste liquid is continued to employ, about 500mL, and after testing, wherein the soluble silicon species are (with SiO
2Meter) mass content is 2%, and the soluble titanium species are (with TiO
2Meter) mass content is 0.05%, and alkaline template agent is (with NH
3Meter) mass content is 1%.
Comparative Examples 2
The X-1 sample of Comparative Examples 1 preparation is in the phenol hydroxylation reaction, and phenol and hydrogen peroxide mol ratio with acetone are solvent at 3: 1, and 80 ℃ are reacted 4h down, catalyst is separated from reaction system, drying is used further to next round reaction, and so circulating, activity is lower than 80% of original activity after 5 times.With catalyst separation, drying obtains the inactivation sample and is designated as S-1.S-1 obtains the roasting regeneration sample through 550 ℃ of roasting 3h then, is designated as B-1.
Comparative Examples 3
This Comparative Examples is the inactivation situation that the molecular sieve catalyst X-1 of 1 of Comparative Examples is used for the cyclohexanone oxamidinating reaction.
Getting TS-1 molecular sieve X-1 places in 100mL band continuous feed and the membrane separation device slurry bed reactor, under stirring, add water mixture (volume ratio of water and hydrogen peroxide is 10: 9) with the hydrogen peroxide of 30wt% with the speed of 5.7mL/h, the mixture (volume ratio of cyclohexanone and the tert-butyl alcohol is 1: 2.5) that adds cyclohexanone and the tert-butyl alcohol with the speed of 10.5mL/h, speed with 5.7mL/h adds 25wt% ammoniacal liquor, above-mentioned three bursts of material flow are for adding simultaneously, simultaneously with the continuous discharging of corresponding speed, reaction temperature maintains 80 ℃, analyzes with chromatogram every the product sampling of 12h after the stable reaction.After after a while, the cyclohexanone conversion ratio drops to 50% by initial 95%, isolates catalyst then and is dried, and is designated as S-2, and drying sample S-2 in 560 ℃ of roasting 4h, gets the roasting regeneration sample under air atmosphere, be designated as B-2.
Comparative Examples 4
Process and the result of alkali treatment only used the S-2 sample of Comparative Examples 3 in the explanation of this Comparative Examples.
Sample S-16g mixes with 16.3%TPAOH solution 20g, water 18g, in sealing and the autoclave, handles 36h at 160 ℃, products therefrom after filtration, washing, drying, through 560 ℃ of roasting 5h, sample is designated as C-1 again.
Embodiment 1
Silicic acid orthocarbonate, the tetraethyl titanate of metering are mixed with TMAH, and adding distilled water, mix the back in stirring at normal temperature 1.0h hydrolysis, and then at 75 ℃ of following 3h that stir, obtain reclaimed rubber, its mole consists of silicon: titanium: organic base: water=1: 0.02: 0.75: 20 (silicon and titanium are respectively with SiO
2And TiO
2Meter, organic base is with NH
3Meter, down with), then with reclaimed rubber and filtrated stock according to mass ratio be 100: 10 ratio mix a mixed liquor; Then deactivated molecular sieve sample S-1 is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 40, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, in sealing autoclave in 145 ℃ of reaction 60h.With gained through the molecular sieve of steam treatment regeneration in 180 ℃ of oven dry 120min, then at 580 ℃ of roasting temperature 5h, obtain regeneration TS-1 molecular sieve-4 A.
Embodiment 2
The Z type silica gel of metering is mixed with TPAOH, and adding distilled water, mix the back in stirring at normal temperature 1.0h, add butyl titanate again and stir 0.5h, then stir 6h down at 65 ℃, obtain reclaimed rubber, its mole consists of silicon: titanium: organic base: water=1: 0.025: 0.8: 20, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 50 ratio mix a mixed liquor; Then sieve sample B-1 after the roasting is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 50, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 175 ℃ of reaction 48h.Products therefrom in 135 ℃ of oven dry 180min, then at 500 ℃ of roasting temperature 6h, is obtained regeneration TS-1 molecular sieve B.
Embodiment 3
Positive tetraethyl orthosilicate, tetraethyl titanate, tetraethyl ammonium hydroxide and the n-butylamine of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h hydrolysis, and then at 70 ℃ of following 4h that stir, obtain reclaimed rubber, its mole consists of silicon: titanium:: tetraethyl ammonium hydroxide: n-butylamine: water=1: 0.02: 0.35: 0.3: 25, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 40 ratio mix a mixed liquor; Then deactivated molecular sieve sample S-2 is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 20, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 160 ℃ of reaction 65h.Products therefrom in 100 ℃ of oven dry 300min, then at 650 ℃ of roasting temperature 4h, is obtained regeneration TS-1 molecular sieve C.
Embodiment 4
Amorphous silica gel, titanium propanolate, triethanolamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, then stir 3h down at 75 ℃ again, obtain reclaimed rubber, its mole consists of silicon: titanium: triethanolamine: TPAOH: water=1: 0.03: 0.25: 0.6: 30, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 20 ratio mix a mixed liquor; Then sieve sample B-2 after the roasting is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 30, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 155 ℃ of reaction 58h.Products therefrom in 150 ℃ of oven dry 180min, then at 580 ℃ of roasting temperature 5h, is obtained regeneration TS-1 molecular sieve D.
Embodiment 5
Z type silica gel, butyl titanate, ethylenediamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.5h, and then at 60 ℃ of following 5h that stir, obtain reclaimed rubber, its mole consists of silicon: titanium: ethylenediamine: TPAOH: water=1: 0.02: 0.15: 0.2: 20, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 200 ratio mix a mixed liquor; Then deactivated molecular sieve sample S-1 is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 80, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining and add in the support of packing into, then in sealing autoclave in 160 ℃ of reaction 48h.Products therefrom in 100 ℃ of oven dry 270min, then at 550 ℃ of roasting temperature 3h, is obtained regeneration TS-1 molecular sieve E.
Embodiment 6
Positive tetraethyl orthosilicate, the tetraethyl titanate of metering are mixed with tetraethyl ammonium hydroxide, and adding distilled water, mix the back in stirring at normal temperature 1.0h, then stir 4h down at 70 ℃ again, obtain reclaimed rubber, its mole consists of silicon: titanium: organic base: water :=1: 0.02: 1.55: 25, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 20 ratio mix a mixed liquor; Then deactivated molecular sieve sample S-2 is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 30, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining and add in the support of packing into, and under it, add water 3mL, in sealing autoclave, react 52h in 165 ℃ then.Products therefrom in 140 ℃ of oven dry 120min, then at 550 ℃ of roasting temperature 3h, is obtained regeneration TS-1 molecular sieve F.
Embodiment 7
Positive tetraethyl orthosilicate, butyl titanate, di-n-propylamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, and then at 75 ℃ of following 3h that stir, obtain reclaimed rubber, it consists of silicon: titanium: di-n-propylamine:: TPAOH: water=1: 0.02: 0.25: 0.5: 25, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 10 ratio mix a mixed liquor; Then sieve sample B-1 after the roasting is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 60, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 180 ℃ of reaction 12h.Products therefrom in 120 ℃ of oven dry 240min, then at 700 ℃ of roasting temperature 3h, is obtained regeneration TS-1 molecular sieve G.
Embodiment 8
Z type silica gel, the positive ester of metatitanic acid, hexamethylene diamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, and then at 75 ℃ of following 3h that stir, obtain reclaimed rubber, its mole consists of silicon: titanium: hexamethylene diamine: TPAOH: water=1: 0.02: 0.75: 1.0: 30, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 100 ratio mix a mixed liquor; Then sieve sample B-2 after the roasting is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 70, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining of packing into, then in sealing autoclave in 155 ℃ of reaction 65h.Products therefrom in 100 ℃ of oven dry 300min, then at 550 ℃ of roasting temperature 5h, is obtained regeneration TS-1 molecular sieve H.
Embodiment 9
Positive tetraethyl orthosilicate, titanium propanolate, n-propylamine and the tetraethyl ammonium hydroxide of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, and then at 75 ℃ of following 3h that stir, obtain reclaimed rubber, its mole consists of silicon: titanium: n-propylamine: tetraethyl ammonium hydroxide: water=1: 0.045: 1.0: 1.0: 20, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 10 ratio mix a mixed liquor; Then deactivated molecular sieve sample S-1 is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 40, with its 50mL polytetrafluoroethyllining lining and be placed on the 100mL polytetrafluoroethyllining lining and add in the support of packing into, under it, add water 5mL simultaneously.In sealing autoclave, react 45h in 175 ℃ then.Products therefrom in 160 ℃ of oven dry 180min, then at 550 ℃ of roasting temperature 3h, is obtained regeneration TS-1 molecular sieve I.
Embodiment 10
Amorphous Si O with metering
2, tetraethyl ammonium hydroxide and TPAOH mix, and adding distilled water, stirring at normal temperature 2h, stir 3h down at 75 ℃ again, obtain reclaimed rubber, its mole consists of silicon: tetraethyl ammonium hydroxide: TPAOH: water :=1: 0.5: 0.2: 45, then with reclaimed rubber and filtrated stock according to mass ratio be 100: 250 ratio mix a mixed liquor; Then sieve sample B-1 after the roasting is mixed with the mass ratio of above-mentioned mixed liquor according to 100: 50, its 100mL polytetrafluoroethyllining lining of packing into is also put into the vial of adorning 2mL water thereon, in sealing autoclave, react 56h in 160 ℃ then.With gained in product in 100 ℃ of oven dry 270min, then at 570 ℃ of roasting temperature 5h, obtain regeneration TS-1 molecular sieve J.
Test case
This test case illustrates the regeneration effect of the inventive method with the effect of phenol hydroxylation reaction.
The HTS sample that above-described embodiment 1～10 regeneration is obtained and the HTS sample of Comparative Examples 1～4, according to HTS: phenol: the weight ratio of acetone=1: 20: 16 mixes in the there-necked flask of a band condenser pipe, be warming up to 80 ℃, then under stirring according to phenol: it is the hydrogen peroxide of 30wt% that the mol ratio of hydrogen peroxide=3: 1 adds concentration, under this temperature, react 4h, products therefrom uses the HP-5 capillary column at 6890N type gas chromatograph, and (30m * 0.25mm) measure phenol conversion the results are shown in Table 1.
Table 1
| The sample name | Molecular sieve yield % | Relative crystallinity Rc% | Phenol conversion % |
| X-1 | 82 | 100 | 24.5 |
| S-1 | 86 | 42 | 10.6 |
| B-1 | 85 | 91 | 22.4 |
| S-2 | 81 | 74 | 14.8 |
| B-2 | 85 | 86 | 20.9 |
| C-1 | 91 | 93 | 22.7 |
| A | 95 | 99 | 24.4 |
| B | 98 | 98 | 24.5 |
| C | 99 | 105 | 24.2 |
| D | 97 | 99 | 24.0 |
| E | 97 | 99 | 24.5 |
| F | 99 | 101 | 24.1 |
| G | 97 | 99 | 23.9 |
| H | 99 | 97 | 24.6 |
| I | 98 | 104 | 24.5 |
| J | 98 | 103 | 24.3 |
From table 1 data as can be seen, the HTS specific activity deactivated titanium silicon molecular sieve activity of method provided by the invention regeneration has had and has significantly improved, and reaches fresh dose activity level substantially.Relative crystallinity R
CAlso be restored, illustrate and adopt the inventive method regeneration back framework of molecular sieve integrity degree to be maintained and recover.Simultaneously, yield also is improved.
Claims (11)
1. the processing method of a deactivated titanium silicon molecular sieve, the filtrated stock that a kind of reclaimed rubber and HTS building-up process are obtained mixes and obtains mixed liquor, again described mixed liquor is contacted and places under the closed reactor hydrothermal condition with the HTS of inactivation and handle, then at normal temperatures and pressures with the product drying, the HTS that roasting obtains regenerating, wherein, described reclaimed rubber contains the silicon source, titanium source and organic base, contain in the described closed reactor under reaction condition form saturated steam and with the weight ratio of the HTS of inactivation less than 1.2 the water yield, the treating capacity of the HTS of inactivation is 10g/L reactor volume at least.
2. according to the process of claim 1 wherein, the mole that described reclaimed rubber contains silicon source, titanium source and organic base consists of the silicon source: titanium source: organic base=(0.1～1): (0～0.1): (0.01～5), the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, organic base is with NH
3Meter, the HTS of inactivation and the weight ratio of mixed liquor are 100: (10～120).
3. according to the method for claim 1, wherein, the mole of described reclaimed rubber consists of the silicon source: titanium source: organic base=1: (0.01～0.05): (0.3～3), the mass ratio of the filtrated stock that described reclaimed rubber and HTS building-up process obtain is 100: (10～500), the weight ratio of deactivated titanium silicon molecular sieve and mixed liquor are 100: (30～100).
4. according to the process of claim 1 wherein, described deactivated titanium silicon molecular sieve is TS-1, TS-2, Ti-Beta, the Ti-MWW molecular sieve of inactivation.
5. according to the method for claim 1 or 3, wherein, described deactivated titanium silicon molecular sieve comes from alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating or alkane oxidation reaction.
6. according to the process of claim 1 wherein, the water yield in the described reactor is provided by the reaction kettle for reaction material, or realizes through adding outside steam.
7. according to the method for claim 1, wherein, described organic base is selected from one or more in TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine and the triethanolamine.
8. according to the process of claim 1 wherein, it is R that described silicon source is selected from silica, silica gel or general formula
1 4SiO
4The organosilicon acid esters, R
1Be selected from the alkyl of 1～4 carbon atom.
9. according to the process of claim 1 wherein, described titanium source is selected from TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2, or general formula is Ti (OR
2)
4Organic titanate, R
2Be selected from the alkyl of 2～4 carbon atoms.
10. according to the process of claim 1 wherein, the filtrated stock that described HTS building-up process obtains contains soluble silicon species, soluble titanium species and alkaline template agent, with SiO
2Count described soluble silicon species mass content＜10%, with TiO
2Count described soluble titanium species mass content＜1%, with NH
3Count described alkaline template agent mass content＜15%.
11. according to the method for claim 1, it is characterized in that deactivated titanium silicon molecular sieve and a kind of preparation HTS gained are filtered waste liquid contact with reclaimed rubber mix before, pass through calcination process earlier.
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