CN103182320A - Regeneration method of titanium-silicon molecular sieve - Google Patents
Regeneration method of titanium-silicon molecular sieve Download PDFInfo
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Abstract
The invention relates to a regeneration method of a titanium-silicon molecular sieve. The method is characterized by: mixing a regeneration liquid with a filtered stock of a titanium-silicon molecular sieve synthesis process to obtain a mixed solution, contacting the mixed solution with a deactivated titanium-silicon molecular sieve, putting them in a closed reaction kettle to undergo a hydrothermal treatment, and recovering the regenerated titanium-silicon molecular sieve. The titanium-silicon molecular sieve regenerated by the method has activity equal to that of a fresh agent. The method is green and efficient, and has a high yield.
Description
Technical field
The invention relates to a kind of method of the HTS of regenerating.
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.
People such as Italy Taramasso disclose the preparation method (GB2071071A, 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 oxidation operation reaction, its renovation process mainly concentrates on conventional 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 use hydrogen peroxide treatment 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 HTS Ti-MWW 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.
Summary of the invention
In the technology of existing preparation HTS for example among USP4410501 and " Zeolites; 1992; Vol.12:943 ", the utilization rate in silicon source is about 75～95%, and template agent utilization rate is about 20～95%, has the template agent of 5～25% silicon and 5～80% to be retained in so approximately and does not obtain in the filtrated stock (filtration waste liquid) utilizing, if as direct discharging of waste water, not only cause very big waste, and can pollute environment, do not meet the requirement of environmental protection and sustainable development.
The present inventor is surprised to find that in the experiment of a large amount of regeneration HTSs, when carrying out hydrothermal treatment consists with this filtrated stock with the titanium-silicon molecular sieve catalyst to inactivation after a kind of regenerated liquid mixes, the HTS specific activity deactivated molecular sieve activity that obtains of regenerating like this improves greatly, activity can return to fresh dose of level of former HTS, and the regenerative process material consumption is low, the yield height also reduces synthetic waste liquid to the pollution of environment.This method can also be saved cost.More surprisingly, this its relative crystallinity of method gained sample also is restored.Based on this, finish the present invention.
The objective of the invention is to provide on the basis of existing technology a kind of more efficiently method that deactivated titanium silicon molecular sieve is regenerated, this method regenerative process yield height, cost is low, especially has good regeneration effect for deactivated titanium silicon molecular sieve such as run off because of the activated centre, skeleton caves in, the HTS activity of regeneration can return to fresh dose level, and the relative crystallinity of the HTS after the regeneration also is restored simultaneously.
The method of regeneration HTS provided by the invention, it is characterized in that a kind of regenerated liquid is mixed the mixed liquor that obtains with the filtrated stock of HTS building-up process to be contacted with the HTS of inactivation, place the closed reactor hydrothermal treatment consists, reclaim the HTS that obtains regenerating.
Renovation process provided by the invention, under pressure, deactivated molecular sieve is being handled in airtight container with the material that contains silicon, titanium and organic base, the allogene that can will get lodged in the molecular sieve crystal micropore fully discharges, the mediation duct, and can better repair framework of molecular sieve, remedy or repair the activated centre of partial loss, its activity can maintain an equal level with fresh dose of activity, the silicon and the titanium that add can enter into framework of molecular sieve, have improved the regenerated molecular sieve product yield.Particularly utilize HTS synthetic " waste liquid " as the partial regeneration raw material, not only saved raw material, can also make refuse obtain utilizing, reduced in the HTS building-up process pollution to environment, green high-efficient.In addition, its relative crystallinity of the inventive method gained sample also is restored.
The specific embodiment
The method of regeneration HTS provided by the invention, it is characterized in that a kind of regenerated liquid is mixed the mixed liquor that obtains with the filtrated stock of HTS building-up process to be contacted with the HTS of inactivation, place the closed reactor hydrothermal treatment consists, reclaim the HTS that obtains regenerating.
We know, HTS is as catalyst, after in organic oxidation reaction such as alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating or alkane oxidation reaction (for example phenol hydroxylation, cyclohexanone oxamidinating, epoxidation of propylene), 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 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 12% below from 25%) without phenol conversion after the recycling utilization five times, i.e. catalyst generation 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 occur for the treatment of alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating or alkane oxidation reaction 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 conventional regeneration such as roasting, solvent wash, adopt method provided by the invention can obtain satisfied regeneration effect, and the process green high-efficient.
In the method provided by the invention, described regenerated liquid mixes (hydrolysis) with organic base solution, silicon source, titanium source and obtains, the mole of regenerated liquid consists of the silicon source: titanium source: organic base: water=(0.01～1): (0.001～0.1): (0.01～0.5): (5～100), preferred mole consists of (0.05～0.5): (0.001～0.025): (0.01～0.25): (5～60) wherein the silicon source with SiO
2Meter, the titanium source is with TiO
2Meter, organic base is with NH
3Meter.The mass ratio of the filtrated stock of described regenerated liquid and HTS building-up process is 100: (1～50000); The HTS of described inactivation and the part by weight of described mixed liquor are 1: (1～25).
In the method provided by the invention, described organic base 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 fat amine compound can be ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine or hexamethylene diamine etc., and described alcamine compound can be MEA, diethanol amine or triethanolamine.Described organic base also can be selected from TPAOH, tetraethyl ammonium hydroxide, TMAH, TBAH, ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine, in the triethanolamine one or more, for example, 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 all can be used for the present invention.
In the method provided by the invention, described silicon source 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, described titanium source 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 filtrated stock refers to synthesis mother liquid, be after HTS utilizes traditional water thermal synthesis crystallization method synthetic, product is carried out remaining liquid after Separation of Solid and Liquid goes out the HTS product, because the general mode of filtering that adopts is separated, filter waste liquid or filter stoste so also can be described 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 treatment conditions are 90～200 ℃ of following hydrothermal treatment consists 2～144h in closed reactor, preferably at 135～180 ℃ of following hydrothermal treatment consists 6～72h.Described removal process is familiar with by those skilled in the art; at this and have no special requirements; usually reclaim the process that comprises filtration, washing, drying and roasting; described dry run can be carried out under the temperature between room temperature～200 ℃, described roasting can be between 300 ℃～800 ℃ in air atmosphere 2～12h carry out.
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 RC of sample is the X-ray diffraction mensuration of carrying out sample at Siemens D5005 type x-ray diffractometer, and 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, is authentic specimen with Comparative Examples 1 sample here.The relative crystallinity RC data of each sample see Table 1.
Comparative Examples 1
This Comparative Examples is according to the TS-1 sample of the method preparation of document US P4410501 record, is designated as X-1, filter waste liquid and continue to employ, and about 2000mL, 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 used for the phenol hydroxylation reaction, and phenol and hydrogen peroxide mol ratio 3: 1 are solvent with acetone, 80 ℃ are reacted 4h down, catalyst is separated drying from reaction systems, be used further to next round reaction, 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, drying, and the sieve sample of inactivation is designated as S-2 by the time.Again under 550 ℃ under air atmosphere roasting S-2 sample 5h, obtain the sample of roasting regeneration, sample is designated as B-2.
Comparative Examples 4
The explanation of this Comparative Examples is only regenerated the S-2 sample of Comparative Examples 3 with the alkali treatment mode process.
6g sample S-2 mixes with 20gTPAOH solution (16.3%), 18g water, 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
Present embodiment illustrates the method for regeneration HTS provided by the invention.
The amorphous silica gel of metering is mixed with TPAOH, and adding distilled water, mix the back in stirring at normal temperature 1.5h, add butyl titanate again and stir 0.5h, then stir 3h down at 75 ℃, make regenerated liquid, it consists of silicon (mol): titanium (mol): organic base (mol): water (mol)=0.05: 0.001: 0.15: 20 (wherein silicon and titanium are with SiO
2And TiO
2Meter, organic base is with NH
3Meter), regenerated liquid and a certain amount of filtrated stock (coming from Comparative Examples 1, down together) that obtains mixed, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 15.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 60g, in sealing autoclave, react 52h in 175 ℃ then.With products therefrom after filtration, the washing, in 180 ℃ the oven dry 120min, then at 650 ℃ of roasting temperature 2h, the molecular sieve-4 A that obtains regenerating.
Embodiment 2
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Silester, 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, stir down 3h at 65 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): organic base (mol): water (mol)=0.01: 0.0005: 0.2: 35 (wherein silicon and titanium are with SiO
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 5.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 80g, in sealing autoclave, react 72h in 160 ℃ then.With products therefrom after filtration, the washing, in 135 ℃ the oven dry 120min, then at 500 ℃ of roasting temperature 6h, the molecular sieve B that obtains regenerating.
Embodiment 3
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Silester, the tetraethyl titanate of metering are mixed with tetraethyl ammonium hydroxide, monoethanolamine, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir 3h down at 75 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): tetraethyl ammonium hydroxide (mol): monoethanolamine (mol): water (mol)=0.1: 0.01: 0.08: (wherein silicon and titanium were with SiO in 0.05: 20
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 150.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 100g, in sealing autoclave, react 12h with 140 ℃ then.With products therefrom after filtration, washing, in 100 ℃ of oven dry 300min, then at 580 ℃ of roasting temperature 4h, obtain regeneration TS-1 molecular sieve C.
Embodiment 4
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Z type silica gel, triethanolamine and the TPAOH of metering are mixed, and adding distilled water, in stirring at normal temperature 2h, drip tetrabutyl titanate again, then stir 1h down at 70 ℃ and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): triethanolamine (mol): TPAOH (mol): water (mol)=0.03: 0.0014: 0.1: (wherein silicon and titanium were with SiO in 0.12: 40
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 100.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 120g, in sealing autoclave, react 48h in 165 ℃ then.With products therefrom after filtration, the washing, in 180 ℃ the oven dry 180min, then at 750 ℃ of roasting temperature 2h, the molecular sieve D that obtains regenerating.
Embodiment 5
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Butyl silicate, the titanium propanolate of metering are mixed with tetraethyl ammonium hydroxide, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir down 2h at 80 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): organic base (mol): water (mol)=0.07: 0.0015: 0.08: 35 (wherein silicon and titanium are with SiO
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 250.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 30g, in sealing autoclave, react 12h in 180 ℃ then.With products therefrom after filtration, the washing, in 100 ℃ the oven dry 270min, then at 650 ℃ of roasting temperature 2h, the molecular sieve E that obtains regenerating.
Embodiment 6
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Silicic acid propyl ester, butyl titanate, the n-butylamine of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir down 1h at 85 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): organic base (mol): water (mol)=0.2: 0.006: 0.35: 80 (wherein silicon and titanium are with SiO
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 25.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 50g, in sealing autoclave, react 8h in 160 ℃ then.With products therefrom after filtration, the washing, in 120 ℃ the oven dry 180min, then at 550 ℃ of roasting temperature 6h, the molecular sieve F that obtains regenerating.
Embodiment 7
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Butyl silicate, tetraethyl titanate, n-propylamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir 2h down at 65 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): n-propylamine (mol): TPAOH (mol): water (mol)=0.45: 0.014: 0.08: (wherein silicon and titanium were with SiO in 0.17: 45
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 2.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 20g, in sealing autoclave, react 48h in 155 ℃ then.With products therefrom after filtration, the washing, in 100 ℃ the oven dry 240min, then at 600 ℃ of roasting temperature 3h, the molecular sieve G that obtains regenerating.
Embodiment 8
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Silester, the titanium propanolate of metering are mixed with TBAH, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir down 2h at 70 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): organic base (mol): water (mol)=0.5: 0.0085: 0.3: 80 (wherein silicon and titanium are with SiO
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 7.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 90g, in sealing autoclave, react 36h in 175 ℃ then.With products therefrom after filtration, the washing, in 140 ℃ the oven dry 120min, then at 570 ℃ of roasting temperature 4h, the molecular sieve H that obtains regenerating.
Embodiment 9
Present embodiment illustrates the method for regeneration HTS provided by the invention.
Silica, n-propylamine and the TPAOH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 2h, drip tetrabutyl titanate again, stir 1h down at 75 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): n-propylamine (mol): TPAOH (mol): water (mol)=0.1: 0.005: 0.12: (wherein silicon and titanium were with SiO in 0.28: 100
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 400.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 30g, in sealing autoclave, react 60h in 155 ℃ then.With products therefrom after filtration, the washing, in 175 ℃ the oven dry 90min, then at 580 ℃ of roasting temperature 4h, the molecular sieve I that obtains regenerating.
Embodiment 10
The present embodiment explanation method of putting off until some time later HTS provided by the invention.
Silicic acid propyl ester, tetraethyl titanate, tetraethyl ammonium hydroxide and the TBAH of metering are mixed, and adding distilled water, mix the back in stirring at normal temperature 1.0h, stir 2h down at 75 ℃ again and obtain regenerated liquid, it consists of silicon (mol): titanium (mol): tetraethyl ammonium hydroxide (mol): TBAH (mol): water (mol)=0.3: 0.012: 0.1: (wherein silicon and titanium were with SiO in 0.1: 90
2And TiO
2Meter, organic base is with NH
3Meter), the regenerated liquid that obtains is mixed with a certain amount of filtrated stock, wherein, the mass ratio of regenerated liquid and filtrated stock is 100: 500.Get the above-mentioned mixed liquor mixing of 12g inactivation TS-1 molecular sieve B-1 and 40g, in sealing autoclave, react 56h in 165 ℃ then.With products therefrom after filtration, the washing, in 120 ℃ the oven dry 180min, then at 520 ℃ of roasting temperature 6h, the molecular sieve J that obtains regenerating.
Test case
The TS-1 molecular sieve of this test case explanation embodiment of the invention and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
With the TS-1 molecular sieve of above-described embodiment and Comparative Examples according to TS-1: 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 weight ratio of hydrogen peroxide=1: 0.39 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 | 96 | 98 | 24.5 |
| B | 99 | 99 | 24.7 |
| C | 95 | 98 | 24.2 |
| D | 96 | 101 | 23.9 |
| E | 98 | 97 | 24.5 |
| F | 96 | 99 | 24.1 |
| G | 99 | 98 | 24.0 |
| H | 97 | 99 | 24.6 |
| I | 99 | 103 | 24.3 |
| J | 97 | 99 | 24.2 |
From table 1 data as can be seen, the molecular sieve specific activity deactivated molecular sieve activity that the inventive method is regenerated significantly improves, and maintains an equal level with fresh dose of activity.
Simultaneously as can be seen, the relative crystallinity Rc of molecular sieve also is restored the yield height after the inventive method regeneration in table 1.Illustrate and adopt the inventive method regeneration back framework of molecular sieve integrity degree to obtain repairing and keeping, the yield of handling the back molecular sieve simultaneously improves.
Claims (12)
1. the method for the HTS of regenerating, it is characterized in that a kind of regenerated liquid is mixed the mixed liquor that obtains with the filtrated stock of HTS building-up process to be contacted with the HTS of inactivation, place the closed reactor hydrothermal treatment consists, reclaim the HTS that obtains regenerating.
2. according to the method for claim 1, wherein, described regenerated liquid mixes silicon source, titanium source and obtains with organic base solution, the mole of described regenerated liquid consists of the silicon source: titanium source: organic base: water=(0.01～1): (0.001～0.1): (0.01～0.5): (5～100), wherein the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, organic base is with NH
3Meter, the mass ratio of the filtrated stock of described regenerated liquid and HTS building-up process is 100: (1～50000); The part by weight of the HTS of described mixed liquor and inactivation is (1～25): 1.
3. according to the method for claim 2, wherein, the mole of described regenerated liquid consists of the silicon source: titanium source: organic base: water=(0.05-0.5): (0.001～0.025): (0.01～0.25): (5～60).
4. according to the method for claim 2, wherein, the mass ratio of the filtrated stock of described regenerated liquid and HTS building-up process is 100: (1～10000).
5. according to the method for claim 1 or 2, wherein, the HTS of described inactivation is selected from one or more among the TS-1 of inactivation, TS-2, Ti-Beta or the Ti-MWW.
6. according to the method for claim 5, wherein, the HTS of described inactivation comes from alkene epoxidation, aromatic hydrocarbons hydroxylating, ketone oxamidinating or alkane oxidation reaction.
7. according to the method for claim 2, 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.
8. according to the method for claim 2, 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.
9. according to the method for claim 2, wherein, described organic base is selected from quaternary ammonium base compound, amine compound or alcohol amine compound.
10. according to the method for claim 2, 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.
11. according to the method for claim 1 or 2, wherein, described filtrated stock contains with SiO
2The meter mass content＜10% the soluble silicon species, with TiO
2The meter mass content＜1% titanium species and with NH
3The alkaline template agent of meter mass content＜15%.
12. according to claim 1,2,4 or 11 method, wherein said filtrated stock is from the building-up process of TS-1 molecular sieve.
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