CN102153104A - Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexane oxime by using molecular sieve - Google Patents
Method for preparing titanium-silicon molecular sieve and method for preparing cyclohexane oxime by using molecular sieve Download PDFInfo
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Abstract
The invention provides a method for preparing a titanium-silicon molecular sieve with large particle diameter. The method comprises the following steps of: preparing dispersion liquid of a first-level crystalline particle molecular sieve; adding a flocculating agent and a coagulant aid into the dispersion liquid, and gathering the particles so as to form gathered particle solution; mixing the gathered particle solution and titanium-silicon template synthetic cement; and performing a hydrothermal process. The titanium-silicon molecular sieve prepared by the method has an average particle diameter of more than 5 microns; and when serving as a contact agent for preparing cyclohexane oxime, the titanium-silicon molecular sieve has high conversion rate and selection rate, and has the advantage of easiness for filtering and recycling.
Description
Technical field
The present invention relates to a kind of method for making of titanium-si molecular sieves, particularly a kind of method for making of big particle diameter titanium-si molecular sieves.
Background technology
Crystallization titanium-si molecular sieves is that titanium atom is introduced in the reticulated structure of silicon-dioxide, has the crystalline form of MFI structure, also claims the TS-1 molecular sieve.And this molecular sieve be widely used in the hydrogen peroxide be in the oxidizing reaction of oxygenant as catalyst, its method for making has been exposed in No. 4410501 patent of invention of the U.S..But the sieve particle of this method institute output is approximately 0.2 micron.Yet 0.2 micron catalyst (is that catalyst prepares in the application of cyclohexanone-oxime with the HTS as utilizing reactants such as pimelinketone, ammonia and hydrogen peroxide) in chemical technique is used faces big challenge.Therefore, follow-up inventor all is devoted to develop the technology that strengthens the particle diameter molecular sieve.The U.S. No. 5500199, No. 6106803 and No. 6524984 patent teaching are assembled the small-particle catalyst after spray drying granulation with inorganic sticking agent, though this method can become big with catalyst grains, agent is covered and the diluted reactive behavior that causes of active group is not enough and the essential catalyst consumption that increases because of the catalyst activity base gets adhered but have, and makes the shortcoming of keeping identical catalysis effect.
Therefore, how overcoming above-mentioned shortcoming real has been problem urgently to be separated.Still need a kind of method with big particle diameter and highly active titanium-si molecular sieves for preparing on the industry, it can overcome difficulty that tradition reclaims molecular sieve, promote the hydrogen peroxide service efficiency and be applicable to application on the industry.
Summary of the invention
The disappearance of known technology in view of the above, the present invention promptly provides a kind of method for making of big particle diameter titanium-si molecular sieves, comprising: the dispersion liquid of preparing first step crystalline particle molecular sieve; In above-mentioned dispersion liquid, add flocculation agent and coagulant aids, make particle aggregation, form aggregated particles solution; Mix this aggregated particles solution and titanium-silicon template synthetical glue; And carry out hydrothermal step.Formed titanium-the si molecular sieves of method for making of the present invention has the median size more than 5 microns, when making the catalyst of cyclohexanone-oxime, not only can reach high conversion and selection rate, more with the advantage that is easy to filtering separation.
Embodiment
Below by specific specific examples explanation embodiments of the present invention, the person of ordinary skill in the field can understand advantage of the present invention and effect easily by the content that this specification sheets disclosed.The present invention can also other different mode be implemented, and, under the prerequisite departing from disclosed technological thought not, can give different modifications and change that is.
The molecular sieve of the not calcining molecular sieve powder (TS-1, S-1 or its combination) of hydro-thermal as first step crystalline particle finished in method for making use of the present invention, this first step crystalline particle molecular sieve powder is scattered in forms dispersion liquid in the water, add flocculation agent then and coagulant aids makes particle aggregation, form the aqueous solution of aggregated particles, remix has the aqueous solution and the titanium-silicon template synthetical glue of this aggregated particles, this mixture is sealed in the Teflon inner liner stainless steel autoclave carries out hydrothermal step at last.Usually, the molecular sieve of this first step crystalline particle and this titanium-silicon template synthetical glue blended weight ratio scope was between 1: 10 to 1: 800, and is preferable between 1: 10 to 1: 600, better for 1: 10 to 1: 300, better for again 1: 11.6 to 1: 167.
The employed flocculation agent of method for making of the present invention is a polymeric flocculant.More specifically, flocculation agent kind of the present invention can be selected from cationic flocculant, anionic flocculant, amphoteric flocculating agent or its combination.The example of this cationic flocculant comprises that QAS polymer is (such as dimethyl-diallyl ammonium chloride (ally-ammonium chloride) polymkeric substance or the trimethylammonio polymerizable methacrylate thing of polymethyl acrylic acid (poly (trimethylammonium methacrylate)), poly-second ammonium (polyvinyl ammonium) or polyvinyl pyridine, or its combination; The example of anionic flocculant comprises sodium polyacrylate and acryloyl ammonium (acrylamide) multipolymer, sodium acrylate and acryloyl ammonium multipolymer or its combination; The example of amphoteric flocculating agent comprises the multipolymer of vinylformic acid quaternary ammonium salt and sodium acrylate.Generally speaking, the molecular-weight average of the employed polymeric flocculant of method for making of the present invention is at least more than 100,000, is preferably 100,000 to 20,000,000.This flocculation agent can the aqueous solution mode add.Usually, the concentration of this flocculant aqueous solution (weight percent) scope is 0.1 to 1 weight %, is preferably 0.2 to 0.8 weight %, is more preferred from the scope of 0.3 to 0.6 weight % again.This flocculation agent consumption in the titanium-silicon template synthetical glue of 100 grams, uses 0.0001 to 0.05 gram, is preferably and uses 0.0001 to 0.03 gram, better 0.001 to 0.025 gram that is to use.
Coagulant aids used in the present invention can be silicon ester, polyethoxye silane or dioxide/silica gel liquid solution.The example of this silicon ester comprises tetramethylsilane acid esters, tetraethyl silicane acid esters, silicon tetrapropyl acid esters, tetrabutyl silicane acid esters or its combination; This polyethoxye silane can example comprise ES-28 (n=1 to 2), ES-32 (n=3 to 4), ES-40 (n=4 to 5) or its combination; And the example of this dioxide/silica gel liquid solution comprises Ludox AS-40, Ludox AS-30, Ludox AM-30, Ludox TM-40, LudoxTM-50, Ludox AM-30, Ludox HS-30, Ludox HS-40 or its combination available from E.I.Du Pont Company.In the method for making of the present invention, the usage quantity of this coagulant aids in the titanium-silicon template synthetical glue of 100 grams, is used the coagulant aids of 0.1 to 6 gram, is preferably the coagulant aids that uses 0.1 to 3 gram.
In a specific examples, the employed titanium of method for making of the present invention-silicon template synthetical glue prepares by following method: at first, earlier titanium source (for example, tetraalkyl titanate, titanous chloride, titanium tetrachloride, and titanium sulfate etc.) placed reaction vessel.In this specific examples, be to place nitrogen to seal single neck bottle in this titanium source.Then system temperature is reduced to 5 ℃, solvent (for example, anhydrous isopropyl alcohol or water) is injected above-mentioned nitrogen seal single neck bottle, stirred 15 minutes.Then, utilize isobaric feed hopper that silicon source (for example, tetraalkyl silicon ester, silica gel, silicon sol) splashed into nitrogen and seal in single neck bottle, continue to stir after being added dropwise to complete, last 1 hour.After treating that stirring is finished, utilize isobaric feed hopper that template (for example, TPAOH) is splashed into nitrogen and seal in single neck bottle, continue again after being added dropwise to complete to stir, last 1 hour.At last, treat that system temperature rises again to normal temperature, remove solvent, promptly obtain titanium-silicon template synthetical glue (for example, under 80 ℃ condition, advance shape and remove alcohol, last 2 hours).Generally speaking, the present invention makes in the reaction process of this titanium-silicon template synthetical glue, and the molar ratio range in employed titanium source and silicon source is 0.005: 1 to 0.06: 1, is preferably 0.015: 1 to 0.05: 1, is more preferred from 0.02: 1 to 0.045: 1.The molar ratio range in employed template and silicon source is 0.1: 1 to 0.5: 1, is preferably 0.15: 1 to 0.45: 1, is more preferred from 0.2: 1 to 0.4: 1.The molar ratio range in employed anhydrous isopropyl alcohol and silicon source is 1: 1 to 4.5: 1, is preferably 1.8: 1 to 3.5: 1, is more preferred from 2.2: 1 to 3: 1.The mol ratio in employed water and silicon source is 10: 1 to 80: 1, is preferably 20: 1 to 60: 1, is more preferred from 30: 1 to 50: 1.
In the method for making of the present invention, this hydrothermal step is to utilize water as medium, adds suitable temperature, produces pressure in airtight reactor, reacts.In one action body example, the present invention is by hydrothermal method, utilizes Teflon inner liner stainless steel autoclave as reactor, with reactor screw, airtight after, put into process furnace and react, make big particle diameter titanium-si molecular sieves.Generally speaking, the temperature of the hydrothermal step that method for making of the present invention is carried out is preferably 150 ℃ to 180 ℃ between 100 ℃ to 220 ℃.The time range of hydrothermal step is 72 hours to 240 hours, is preferably 120 hours to 192 hours.
Method for making of the present invention also can be after hydrothermal step be finished, and with solid and liquid separation, solid part to be to be washed to neutrality, and drying and calcining again obtains to be used for the big particle diameter titanium-si molecular sieves catalyst of cyclohexanone-oxime.In general, calcining temperature is preferably 500 ℃ to 550 ℃ between 450 ℃ to 650 ℃, and calcination time was preferably 12 hours to 36 hours between 6 hours to 48 hours.
The median size of titanium-si molecular sieves that method of the present invention is prepared can reach more than 5 microns, is suitable for preparing in the technology of cyclohexanone-oxime as catalyst.The present invention also provides a kind of method for preparing cyclohexanone-oxime, and this method uses big particle diameter titanium-si molecular sieves that method for making of the present invention obtained as catalyst, under the condition that solvent exists, with pimelinketone, ammonia, and hydrogen peroxide react, make the cyclohexanone-oxime product.Usually, this reaction is under 1 normal atmosphere or higher pressure, in 40 ℃ to 110 ℃ temperature range, is preferably in 50 ℃ to 90 ℃ temperature range and reacts.In this reaction, employed big particle diameter molecular sieve catalyst accounts for 0.1 to 10 weight % of reaction-ure mixture, is preferably to account for 1 to 5 weight %.The molar ratio range of ammonia and pimelinketone is 1.2: 1 to 2: 1, is preferably 1.4: 1 to 1.8: 1; The molar ratio range of hydrogen peroxide and pimelinketone is 0.7: 1 to 2.0: 1, is preferably 1.0: 1 to 1.5: 1.Employed hydrogen peroxide concentration can be 30% to 50%, and the charging of this hydrogen peroxide can and add in the above-mentioned reactive system progressively along with the reaction times increase.The present invention prepares the reaction of cyclohexanone-oxime and can carry out under the condition that solvent exists, and generally uses polar solvent, for example, alcohols, ketone and water etc., wherein,, preferable as the 3rd butanols again with alcohols.
Being the illustrative of the various embodiments of the inventive method below, is not in order to limit the scope of the invention.
Preparation example 1
Earlier 500 milliliters of round-bottomed flasks are carried out the nitrogen envelope in vacuum system, get 1.98 gram tetra-n-butyl titanic acid ester and add nitrogen envelope round-bottomed flask, temperature is cooled to 5 ℃.Then, inject above-mentioned nitrogen envelope round-bottomed flask, begin simultaneously to stir with injection tube with the anhydrous isopropyl alcohol of 20 grams.After treating temperature equilibrium, get 30 gram tetraethyl silicane acid esters, dropwise add in the nitrogen envelope round-bottomed flask, be added dropwise to complete the back and stirred 1 hour with isobaric charging system.Get 28 grams (40%) four n-propyl ammonium hydroxide aqueous solution, dropwise add in the nitrogen envelope round-bottomed flask, be added dropwise to complete the back and stirred 1 hour with isobaric charging system.Make system rise again to room temperature, restir 1 hour removes alcohol down after 2 hours at 80 ℃ at last, and adding water to gross weight is that 100 grams can be finished titanium-silicon template synthetical glue.
Reference examples 1
The titanium that this preparation example 1 is obtained-silicon template synthetical glue is enclosed in the Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, with pure water washing solid part to neutrality.In 100 ℃ of dryings, calcined 24 hours for 500 ℃, obtain contrast catalyst sample 1, (median size is 1.1 microns, particle diameter meta numerical value (d
50) be titanium-si molecular sieves of 0.5 micron).
Embodiment 1
Get 0.8 gram and do not calcine titanium-silicalite TS-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 3.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 1.5 gram tetramethylsilane acid esters after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 1.(median size is 24.2 microns, particle diameter meta numerical value (d
50) be 15.3 microns)
Embodiment 2
Take 0.7 gram and do not calcine titanium-silicalite TS-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 2.(median size is 8.9 microns, particle diameter meta numerical value (d
50) be 8.24 microns)
Embodiment 3
Take 0.7 gram and do not calcine titanium-silicalite TS-1, be scattered in 40 ml waters in the mode that stirs, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 0.2 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 192 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 3.(median size is 14.7 microns, and particle diameter meta numerical value (d50) is 11.9 microns)
Embodiment 4
Take 0.7 gram and do not calcine titanium-silicalite TS-1, be scattered in 40 ml waters in the mode that stirs, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 1.068 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 4.(median size is 8.4 microns, particle diameter meta numerical value (d
50) be 7.8 microns)
Embodiment 5
Take 8.64 grams and do not calcine titanium-silicalite TS-1, be scattered in 40 ml waters in the mode that stirs, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 160 ℃ of hydro-thermals 240 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves catalyst sample 5.(median size is 5.9 microns, particle diameter meta numerical value (d
50) be 5.3 microns)
Embodiment 6
Take 0.6 gram and do not calcine titanium-silicalite TS-1, in the mode that stirs it is scattered in 40 ml waters, cationic flocculant (the dimethyl-diallyl ammonium chloride polymkeric substance that adds 0.2 milliliter of 0.5 weight %, molecular-weight average is 8,000,000 to 12,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 6.(median size is 15.3 microns, particle diameter meta numerical value (d
50) be 13.1 microns)
Embodiment 7
Take 0.6 gram and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 0.2 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 7.(median size is 12.6 microns, particle diameter meta numerical value (d
50) be 9.9 microns)
Embodiment 8
Take 8.64 grams and do not calcine si molecular sieves S-1, be scattered in 40 ml waters in the mode that stirs, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 168 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 8.(median size is 10.4 microns, particle diameter meta numerical value (d
50) be 8.1 microns)
Embodiment 9
Take 2.16 grams and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 1.06 gram AS-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 9.(median size is 9.3 microns, particle diameter meta numerical value (d
50) be 6.9 microns)
Embodiment 10
Take 2.16 grams and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.4244 gram tetramethylsilane acid esters after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 10.(median size is 6.5 microns, particle diameter meta numerical value (d
50) be 5.7 microns)
Embodiment 11
Take 2.16 grams and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 weight %, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.4180 gram tetraethyl silicane acid esters after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 11.(median size is 8.2 microns, particle diameter meta numerical value (d
50) be 6.6 microns)
Embodiment 12
Take 0.6 gram and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, cationic flocculant (the dimethyl-diallyl ammonium chloride polymkeric substance that adds 0.2 milliliter of 0.5 weight %, 8,000,000 to 12,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 170 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 12.(median size is 8.5 microns, particle diameter meta numerical value (d
50) be 7.5 microns catalyst)
Embodiment 13
Take 8.64 grams and do not calcine si molecular sieves S-1, in the mode that stirs it is scattered in 40 ml waters, cationic flocculant (the dimethyl-diallyl ammonium chloride polymkeric substance that adds 1.5 milliliter of 0.5 weight %, 8,000,000 to 12,000,000) aqueous solution adds 1.061 gram AS-40 after stirring 1 hour, restir promptly formed aggregated particles suspension in 1 hour.
Above-mentioned aggregated particles suspension is mixed stirring 1 hour with the titanium-silicon template synthetical glue of 100 gram preparation examples 1, this mixed solution is enclosed in the Teflon inner liner stainless steel autoclave then, in 180 ℃ of hydro-thermals 120 hours, after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, promptly obtain titanium-si molecular sieves sample 13.(median size is 9.7 microns, particle diameter meta numerical value (d
50) be 7.6 microns)
Embodiment 14
As catalyst, the preparation of carrying out cyclohexanone-oxime is to assess its activity with above-mentioned reference examples 1 and embodiment 1 to 13 formed titanium-si molecular sieves sample.
At first, respectively get 0.55 gram catalyst sample and place three-necked bottle, add 28% ammoniacal liquor of 5 gram pimelinketone and 5.43 grams, load onto prolong and stirring system.After temperature of reaction risen to 60 ℃, add the aqueous solution of 35 weight % hydrogen peroxide of 5.43 grams steppingly with the reaction times, carry out the preparation feedback of cyclohexanone-oxime.After the hydrogen peroxide charging is finished 1 hour, each catalyst is separated with its reaction solution, and each reaction solution after this separation is carried out the analysis of cyclohexanone-oxime.Its analytical results such as table 1:
Table 1
| *C Anoe | **S Oxime/Anoe | ***C H2O2 | ?****S Oxime/H2O2 | Median size (micron) | |
| Reference examples 1 | 99.75％ | 98.28％ | 99.91％ | 88.75％ | 1.1 |
| Embodiment 1 | 99.27％ | 99.99％ | 99.26％ | 91.40％ | 24.2 |
| Embodiment 2 | 99.25％ | 99.57％ | 99.53％ | 90.31％ | 8.9 |
| Embodiment 3 | 99.63％ | 99.25％ | 98.92％ | 90.87％ | 14.7 |
| Embodiment 4 | 99.14％ | 99.66％ | 99.99％ | 89.82％ | 8.4 |
| Embodiment 5 | 99.35％ | 99.52％ | 99.36％ | 90.15％ | 5.9 |
| Embodiment 6 | 99.67％ | 99.03％ | 98.97％ | 91.50％ | 15.3 |
| Embodiment 7 | 99.02％ | 99.24％ | 99.97％ | 89.39％ | 12.6 |
| Embodiment 8 | 99.21％ | 98.49％ | 99.21％ | 89.50％ | 10.4 |
| Embodiment 9 | 99.53％ | 98.92％ | 99.35％ | 90.48％ | 9.3 |
| Embodiment 10 | 98.65％ | 98.37％ | 98.79％ | 90.30％ | 6.5 |
| Embodiment 11 | 97.49％ | 98.89％ | 97.84％ | 90.41％ | 8.2 |
| Embodiment 12 | 99.40％ | 98.84％ | 98.89％ | 92.20％ | 8.5 |
| Embodiment 13 | 99.20％ | 99.21％ | 99.52％ | 89.95％ | 9.7 |
*: C
Anoe=pimelinketone transformation efficiency=pimelinketone consumes mole number/pimelinketone and drops into mole number * 100%
*: S
Oxime/Anoe=cyclohexanone-oxime selection rate=cyclohexanone-oxime output mole number/pimelinketone consumes mole number * 100%
* *: C
H2O2=hydrogen peroxide transformation efficiency=hydrogen peroxide consumes mole number/hydrogen peroxide and drops into mole number * 100%
* * *: S
Oxime/H2O2=hydrogen peroxide selection rate=cyclohexanone-oxime output mole number/hydrogen peroxide consumes mole number * 100%
In sum, the method for making of the big particle diameter titanium-si molecular sieves of the present invention is prepared the big particle diameter molecular sieve that the industry that is beneficial to is used really, and has high catalyst activity according to the prepared big particle diameter molecular sieve of method for making of the present invention.Be applicable to preparation technology such as cyclohexanone-oxime as catalyst according to the prepared big particle diameter molecular sieve of method for making of the present invention, it has cyclohexanone-oxime high selectivity and high conversion, and the high rate of utilization of hydrogen peroxide, more with the advantage that is easy to reclaim.In addition, the median size of the formed big particle diameter titanium-si molecular sieves of the present invention is greater than 5 microns, help separating of follow-up and reaction liquid in the use, do not need to use special filter material, and the median size of titanium-si molecular sieves is controlled at tens of microns and with interior preferable dispersiveness is also arranged in the reaction of slurry formula.
Above-mentioned specification sheets and embodiment only are illustrative principle of the present invention and effect thereof, but not are used to limit the present invention.The scope of the present invention should be listed as claims.
Claims (21)
1. the method for making of a big particle diameter titanium-si molecular sieves is characterized in that, described method for making comprises:
Prepare the dispersion liquid of first step crystalline particle molecular sieve;
In above-mentioned dispersion liquid, add flocculation agent and coagulant aids, make particle aggregation, form aggregated particles solution;
Mix this aggregated particles solution and titanium-silicon template synthetical glue; And
Carry out hydrothermal step.
2. method for making as claimed in claim 1 is characterized in that, this first step crystalline particle molecular screening is from not incinerating titanium-si molecular sieves powder, si molecular sieves powder or its combination.
3. method for making as claimed in claim 1 is characterized in that, this flocculation agent is selected from the flocculation agent of cationic flocculant, anionic flocculant and group that amphoteric flocculating agent is formed for one or more, and the molecular-weight average of this flocculation agent is more than 100000.
4. method for making as claimed in claim 1, it is characterized in that this flocculation agent is selected from the flocculation agent of the group that multipolymer is formed of the multipolymer of multipolymer, sodium acrylate and acryloyl ammonium of dimethyl-diallyl ammonium chloride polymkeric substance, the trimethylammonio polymerizable methacrylate thing of polymethyl acrylic acid, poly-second ammonium, polyvinyl pyridine, sodium polyacrylate and acryloyl ammonium and vinylformic acid quaternary ammonium salt and sodium acrylate for one or more.
5. method for making as claimed in claim 1 is characterized in that, this flocculation agent amount ranges is to count 0.0001 to 0.05 gram with this titanium-silicon template synthetical glue of 100 grams.
6. method for making as claimed in claim 1 is characterized in that, this flocculation agent adds with the flocculant aqueous solution form, and this flocculant aqueous solution concentration is 0.1 to 1 weight %.
7. method for making as claimed in claim 1 is characterized in that, this coagulant aids is selected from the coagulant aids of silicon ester, polyethoxye silane and dioxide/silica gel group that liquid solution is formed for one or more.
8. method for making as claimed in claim 1 is characterized in that, this coagulant aids amount ranges is to count 0.1 to 6 gram with this titanium-silicon template synthetical glue of 100 grams.
9. method for making as claimed in claim 1 is characterized in that, the weight ratio scope of this first step crystalline particle molecular sieve and this titanium-silicon template synthetical glue was between 1: 10 to 1: 800.
10. method for making as claimed in claim 1 is characterized in that, this titanium-silicon template synthetical glue is formed by the following step:
Get the titanium source and place nitrogen envelope reactor;
Solvent is added this nitrogen envelope reactor and mixing;
Silicon source equipressure is splashed into this nitrogen envelope reactor and mixing;
The template equipressure is splashed into this nitrogen envelope reactor and mixing; And
Remove the formation titanium-silicon template synthetical glue that desolvates.
11. method for making as claimed in claim 10 is characterized in that, this titanium source is a tetraalkyl titanate; This silicon source is the tetraalkyl silicon ester; This solvent is an anhydrous isopropyl alcohol; And this template is a TPAOH.
12. method for making as claimed in claim 10 is characterized in that, the mol ratio in this titanium source and silicon source was between 0.005: 1 to 0.06: 1.
13. method for making as claimed in claim 11 is characterized in that, the mol ratio in this anhydrous isopropyl alcohol and silicon source was between 1: 1 to 4.5: 1.
14. method for making as claimed in claim 10 is characterized in that, the mol ratio in this template and silicon source was between 0.1: 1 to 0.5: 1.
15. method for making as claimed in claim 1 is characterized in that, the temperature of this hydrothermal step is between 100 to 220 ℃ scope, and the time of hydrothermal step was between 72 to 240 hours scope.
16. method for making as claimed in claim 1 is characterized in that, described method for making is washed after also being included in hydrothermal step, oven dry and incinerating step.
17. method for making as claimed in claim 1 is characterized in that, the median size of formed big particle diameter titanium-si molecular sieves is greater than 5 microns.
18. a method of making cyclohexanone-oxime, this method utilize the formed big particle diameter titanium-si molecular sieves of the described method for making of claim 1 as catalyst, under the condition that solvent exists, make pimelinketone, ammonia, hydrogen peroxide react the formation cyclohexanone-oxime.
19. method as claimed in claim 18 is characterized in that, the mol ratio of this ammonia and pimelinketone is 1.2: 1 to 2: 1, and the mol ratio of this hydrogen peroxide and pimelinketone is 0.7: 1 to 2.0: 1.
20. method as claimed in claim 18 is characterized in that, this solvent is a polar solvent.
21. method as claimed in claim 18 is characterized in that, the usage quantity of this catalyst accounts for 0.1 to 10 weight % with the total restatement of reactant.
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| CN106276970A (en) * | 2016-09-06 | 2017-01-04 | 四川润和催化新材料股份有限公司 | A kind of SAPO 34 molecular sieve utilizing big particle diameter aluminum source to synthesize and synthetic method thereof and application |
| CN108394974A (en) * | 2018-03-20 | 2018-08-14 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of novel inorganic-organic hybrid flocculant |
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