CN102153104B - 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 large 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 is widely used in and using in the oxidizing reaction that hydrogen peroxide is 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 the catalyst of 0.2 micron (prepares in the application of cyclohexanone-oxime as catalyst as utilized the reactants such as pimelinketone, ammonia and hydrogen peroxide to take HTS) and faces big challenge in chemical technique application.Therefore, follow-up inventor all is devoted to the technology that development strengthens the particle diameter molecular sieve.The U.S. No. 5500199, No. 6106803 and No. 6524984 patent teaching are assembled the small-particle catalyst by spray drying granulation with inorganic sticking agent, though this method can become large by catalyst grains, but there is because the catalyst activity base gets adhered that agent is covered and active group is diluted the not enough and essential catalyst consumption that increases of caused reactive behavior the shortcoming of the catalysis effect that makes to remain identical.
Therefore, how overcoming above-mentioned shortcoming real has been problem urgently to be separated.Still need a kind of method with large particle diameter and highly active titanium-si molecular sieves for preparing on industry, it can overcome difficulty, the lifting hydrogen peroxide service efficiency of tradition recovery molecular sieve and be applicable to the application on industry.
Summary of the invention
The disappearance of known technology in view of the above, the present invention provides a kind of method for making of large particle diameter titanium-si molecular sieves, comprising: the dispersion liquid of preparing first step crystalline particle molecular sieve; Add flocculation agent and coagulant aids in above-mentioned dispersion liquid, 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 manufacturing 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 content disclosed in the present specification.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.
Method for making use of the present invention has completed 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, this first step crystalline particle molecular sieve powder is scattered in water and forms dispersion liquid, then add flocculation agent and coagulant aids to make 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, finally this mixture is sealed in Teflon inner liner stainless steel autoclave and carries out hydrothermal step.Usually, the molecular sieve of this first step crystalline particle with weight ratio scope that this titanium-silicon template synthetical glue mixes between 1: 10 to 1: 800, better for 1: 10 to 1: 600, better for 1: 10 to 1: 300, better for 1: 11.6 to 1: 167 again.
The flocculation agent that method for making of the present invention is used is 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 polymeric flocculant that method for making of the present invention is used 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 % by weight, is preferably 0.2 to 0.8 % by weight, is more preferred from again the scope of 0.3 to 0.6 % by weight.This flocculation agent consumption, in the titanium of 100 grams-silicon template synthetical glue, used 0.0001 to 0.05 gram, is preferably and uses 0.0001 to 0.03 gram, and better is to use 0.001 to 0.025 gram.
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 purchased from E.I.Du Pont Company.In method for making of the present invention, the usage quantity of this coagulant aids, in the titanium of 100 grams-silicon template synthetical glue, 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, prepared by following method by the titanium that method for making of the present invention is used-silicon template synthetical glue: at first, first titanium source (for example, tetraalkyl titanate, titanous chloride, titanium tetrachloride, and titanium sulfate etc.) is placed in to reaction vessel.In this specific examples, be this titanium source to be placed in to nitrogen seal single neck bottle.Then system temperature is down to 5 ℃, solvent (for example, anhydrous isopropyl alcohol or water) is injected to above-mentioned nitrogen and seal single neck bottle, stir 15 minutes.Then, utilize isobaric feed hopper that silicon source (for example, tetraalkyl silicon ester, silica gel, silicon sol) splashed into to nitrogen and seal in single neck bottle, continue to be stirred after being added dropwise to complete, last 1 hour.After having stirred, utilize isobaric feed hopper that template (for example, TPAOH) is splashed into to nitrogen and seal in single neck bottle, after being added dropwise to complete, continue again to be stirred, last 1 hour.Finally, until system temperature, rise again to normal temperature, remove solvent, obtain titanium-silicon template synthetical glue (for example, advance shape except alcohol under the condition of 80 ℃, last 2 hours).Generally speaking, the present invention manufactures in the reaction process of this titanium-silicon template synthetical glue, and the molar ratio range in the He Gui source, titanium source of using 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 the template of using 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 the anhydrous isopropyl alcohol used 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 the water used 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 method for making of the present invention, this hydrothermal step is to utilize water as medium, and additional suitable temperature produces pressure in airtight reactor, is reacted.In one action body example, the present invention is by hydrothermal method, utilizes Teflon inner liner stainless steel autoclave as reactor, by reactor screw, airtight after, put into process furnace and reacted, make large 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, between 100 ℃ to 220 ℃, is preferably 150 ℃ to 180 ℃.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 completes, and by solid and liquid separation, solid part is to be washed to neutrality, then drying and calcining, obtains large particle diameter titanium for cyclohexanone-oxime-si molecular sieves catalyst.In general, calcining temperature, between 450 ℃ to 650 ℃, is preferably 500 ℃ to 550 ℃, and calcination time, between 6 hours to 48 hours, is preferably 12 hours to 36 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 technique of cyclohexanone-oxime as catalyst.The present invention also provides a kind of method for preparing cyclohexanone-oxime, and large particle diameter titanium-si molecular sieves that the method is used method for making of the present invention to obtain is as catalyst, under the condition existed at solvent, with pimelinketone, ammonia, and hydrogen peroxide reacted, make the cyclohexanone-oxime product.Usually, this reaction is under 1 normal atmosphere or higher pressure, in the temperature range of 40 ℃ to 110 ℃, is preferably in the temperature range of 50 ℃ to 90 ℃ and is reacted.In this reaction, the large particle diameter molecular sieve catalyst used accounts for 0.1 to 10 % by weight of reaction-ure mixture, is preferably and accounts for 1 to 5 % by 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.The hydrogen peroxide concentration used can be 30% to 50%, and the charging of this hydrogen peroxide can increase and add progressively in above-mentioned reactive system along with the reaction times.The present invention prepares the reaction of cyclohexanone-oxime and can carry out under the condition of solvent existence, generally uses polar solvent, for example, alcohols, ketone and water etc., wherein, again with alcohols, as better as the 3rd butanols.
Be below the illustrative of the various embodiments of the inventive method, not in order to limit the scope of the invention.
Preparation example 1
First 500 milliliters of round-bottomed flasks are carried out to 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, by the anhydrous isopropyl alcohol of 20 grams, with injection tube, inject above-mentioned nitrogen envelope round-bottomed flask, start to stir simultaneously.After temperature equilibrium, get 30 gram tetraethyl silicane acid esters, with isobaric charging system, dropwise add in nitrogen envelope round-bottomed flask, be added dropwise to complete rear stirring 1 hour.Get 28 gram (40%) four n-propyl ammonium hydroxide aqueous solutions, dropwise add in nitrogen envelope round-bottomed flask with isobaric charging system, be added dropwise to complete rear stirring 1 hour.Make system rise again to room temperature, then stir 1 hour, finally under 80 ℃, remove alcohol after 2 hours, adding water to gross weight is that 100 grams can complete titanium-silicon template synthetical glue.
Reference examples 1
The titanium that this preparation example 1 is obtained-silicon template synthetical glue is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, with pure water washing solid part to neutrality.In 100 ℃ of dryings, calcine 24 hours for 500 ℃, obtain contrast catalyst sample 1, (median size is 1.1 microns, particle diameter meta numerical value (d
50) be the 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 stirred, 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 % by 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, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, 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 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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, in the mode stirred, be scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 0.2 milliliter of 0.5 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 192 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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, in the mode stirred, be scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 1.068 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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, in the mode stirred, be scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 160 ℃ of hydro-thermals 240 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, it is scattered in 40 ml waters, cationic flocculant (dimethyl-diallyl ammonium chloride the polymkeric substance that adds 0.2 milliliter of 0.5 % by weight, molecular-weight average is 8,000,000 to 12,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, 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 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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, in the mode stirred, be scattered in 40 ml waters, the anionic flocculant (sodium acrylate and the acryloyl ammonium multipolymer that add 1.5 milliliter of 0.5 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 168 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, 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 % by weight, molecular-weight average is 15,000,000 to 20,000,000) aqueous solution adds 1.06 gram AS-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, 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 % by 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, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, 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 % by 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, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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 stirred, it is scattered in 40 ml waters, cationic flocculant (dimethyl-diallyl ammonium chloride the polymkeric substance that adds 0.2 milliliter of 0.5 % by weight, 8,000,000 to 12,000,000) aqueous solution adds 0.43 gram ES-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 170 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, obtain titanium-si molecular sieves sample 12.(median size is 8.5 microns, particle diameter meta numerical value (d
50) be the catalyst of 7.5 microns)
Embodiment 13
Take 8.64 grams and do not calcine si molecular sieves S-1, in the mode stirred, it is scattered in 40 ml waters, cationic flocculant (dimethyl-diallyl ammonium chloride the polymkeric substance that adds 1.5 milliliter of 0.5 % by weight, 8,000,000 to 12,000,000) aqueous solution adds 1.061 gram AS-40 after stirring 1 hour, then stirs and within 1 hour, form aggregated particles suspension.
By the titanium of above-mentioned aggregated particles suspension and 100 gram preparation examples 1-silicon template synthetical glue mix and blend 1 hour, then this mixed solution is enclosed in Teflon inner liner stainless steel autoclave, in 180 ℃ of hydro-thermals 120 hours, by after solid and liquid separation, extremely neutral with pure water washing solid part, in 100 ℃ of dryings and 500 ℃ calcining 24 hours, 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
Using above-mentioned reference examples 1 with the formed titanium of embodiment 1 to 13-si molecular sieves sample as catalyst, carry out the preparation of cyclohexanone-oxime to assess its activity.
At first, respectively get 0.55 gram catalyst sample and be placed in 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 is risen to 60 ℃, add steppingly the aqueous solution of 35 % by weight hydrogen peroxide of 5.43 grams with the reaction times, carry out the preparation feedback of cyclohexanone-oxime.After the hydrogen peroxide charging completes 1 hour, each catalyst is separated with its reaction solution, and each reaction solution after this separation is carried out to the analysis of cyclohexanone-oxime.Its analytical results is 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 large particle diameter titanium-si molecular sieves of the present invention is prepared the large particle diameter molecular sieve that is beneficial to the industry application really, and prepared large particle diameter molecular sieve has high catalyst activity according to method for making of the present invention.According to method for making of the present invention, prepared large particle diameter molecular sieve is applicable to preparation technology such as cyclohexanone-oxime as catalyst, and it has cyclohexanone-oxime high selectivity and high conversion, and the high rate of utilization of hydrogen peroxide, more with being easy to the advantage reclaimed.In addition, the median size of the formed large particle diameter titanium-si molecular sieves of the present invention is greater than 5 microns, be conducive in the use separating of follow-up and reaction liquid, 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 better dispersiveness is also arranged in the reaction of slurry formula.
Above-mentioned specification sheets and embodiment are only illustrative principle of the present invention and effect thereof, but not for limiting the present invention.The scope of the present invention, should be as listed as claims.
Claims (13)
1. the method for making of a large 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, wherein, this first step crystalline particle molecular screening is from the titanium of not calcining-si molecular sieves powder, si molecular sieves powder or its combination;
Add flocculation agent and coagulant aids in above-mentioned dispersion liquid, make particle aggregation, form aggregated particles solution, wherein, this flocculation agent is selected from dimethyl-diallyl ammonium chloride polymkeric substance for one or more, the trimethylammonio polymerizable methacrylate thing of polymethyl acrylic acid, poly-ethamine, polyvinyl pyridine, the multipolymer of sodium polyacrylate and acrylamide, the flocculation agent of the group that multipolymer forms of the multipolymer of sodium acrylate and acrylamide and vinylformic acid quaternary ammonium salt and sodium acrylate, this coagulant aids is selected from silicon ester for one or more, the coagulant aids of polyethoxye silane and dioxide/silica gel group that liquid solution forms,
Mix this aggregated particles solution and titanium-silicon template synthetical glue, wherein, this flocculation agent amount ranges is, count 0.0001 to 0.05 gram with this titaniums of 100 grams-silicon template synthetical glue, and the weight ratio scope of this first step crystalline particle molecular sieve and this titanium-silicon template synthetical glue is between 1:10 to 1:800, this titanium-silicon template synthetical glue is formed by the following step: get the titanium source and be placed in nitrogen envelope reactor, solvent is added to this nitrogen envelope reactor and mixes, silicon source equipressure is splashed into to this nitrogen envelope reactor and mixes, the template equipressure is splashed into to this nitrogen envelope reactor and mixes, except desolventizing forms titanium-silicon template synthetical glue, and
Carry out hydrothermal step, the temperature of this hydrothermal step is between the scope of 100 to 220 ℃, and the time of hydrothermal step was between the scope of 72 to 240 hours.
2. 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 % by weight.
3. method for making as claimed in claim 1, is characterized in that, this coagulant aids amount ranges is, with this titaniums of 100 grams-silicon template synthetical glue, counts 0.1 to 6 gram.
4. method for making as claimed in claim 1, is characterized in that, this titanium source is tetraalkyl titanate; This silicon source is the tetraalkyl silicon ester; This solvent is anhydrous isopropyl alcohol; And this template is TPAOH.
5. method for making as claimed in claim 1, is characterized in that, the mol ratio in this Yu Gui source, titanium source is between 0.005:1 to 0.06:1.
6. method for making as claimed in claim 4, is characterized in that, the mol ratio in this anhydrous isopropyl alcohol and silicon source is between 1:1 to 4.5:1.
7. method for making as claimed in claim 1, is characterized in that, the mol ratio in this template and silicon source is between 0.1:1 to 0.5:1.
8. method for making as claimed in claim 1, is characterized in that, the step that described method for making is washed, dried and calcine after also being included in hydrothermal step.
9. method for making as claimed in claim 1, is characterized in that, the median size of formed large particle diameter titanium-si molecular sieves is greater than 5 microns.
10. a method of manufacturing cyclohexanone-oxime, the method utilizes the formed large particle diameter titanium-si molecular sieves of method for making claimed in claim 1 as catalyst, under the condition existed at solvent, makes pimelinketone, ammonia, hydrogen peroxide reacts the formation cyclohexanone-oxime.
11. method as claimed in claim 10, 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.
12. method as claimed in claim 10, is characterized in that, this solvent is polar solvent.
13. method as claimed in claim 10, 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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