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CN102989502A - Preparation method of microspherical catalyst with titanium silicalite molecular sieve - Google Patents

Preparation method of microspherical catalyst with titanium silicalite molecular sieve Download PDF

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CN102989502A
CN102989502A CN2012104894409A CN201210489440A CN102989502A CN 102989502 A CN102989502 A CN 102989502A CN 2012104894409 A CN2012104894409 A CN 2012104894409A CN 201210489440 A CN201210489440 A CN 201210489440A CN 102989502 A CN102989502 A CN 102989502A
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hts
preparation
microspherical catalyst
molecular sieve
catalyst
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王亚权
王书海
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Tianjin University
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Tianjin University
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Abstract

The invention discloses a preparation method of a microspherical catalyst with a titanium silicalite molecular sieve. The preparation method comprises the following steps of: (1) agitating the titanium silicalite molecular sieve with the particle size of 0.1-0.3 micro and silicic acid solution to obtain size; (2) performing spray granulation on the size obtained from the step (1) to prepare microspheres; and (3) calcining the microspheres prepared in the step (2) for 1h-100h at 500-950 DEG C to obtain the microspherical catalyst with the titanium silicalite molecular sieve with the particle size of 5-80 micros. The microspherical catalyst with the titanium silicalite molecular sieve prepared by the method exists in a microspheres manner, has a large particle size and a long service life, does not contain components easily causing decomposition of hydrogen peroxide, and can be used for catalyzing ammoximation of ketones to prepare corresponding ketoxime and catalyzing alkene epoxidation to prepare olefin epoxide; and products are easy to be separated from unreacted reactants, solvents and catalyst in a reaction process.

Description

A kind of preparation method of HTS microspherical catalyst
Technical field
The present invention relates to a kind of HTS microspherical catalyst and preparation method thereof.
Background technology
HTS is a kind of novel selective oxidation catalyst, can be used for the corresponding oxime of catalyzing ketone amidoxime preparation, catalyzing expoxidation of olefines prepares olefin epoxide and the oxidation of catalysis phenols prepares corresponding quinone etc.Use the selective oxidation reaction of titanium molecular sieve catalysis, selectivity of product is high, and accessory substance is few.
It is that template, titanate esters are that titanium source, tetraethyl orthosilicate are that the silicon source is synthetic that the HTS of present function admirable all adopts the tetrapropyl oxyammonia, and particle diameter is 0.1~0.3 μ m (EP0208311, CN1191125C, CN1234683C).The titanium molecular sieve catalysis Performance Ratio of this particle size range is better, but very difficult with separating of product after the reaction.Prepare the HTS of large particle diameter as catalyst, can effectively solve the separation problem of product and catalyst.
US4794198A disclose a kind of employing spot take off (a kind of being stained with that volcanic ash resolves into) mix with HTS after extruded moulding prepare the method for large particle diameter HTS, prepare the cyclohexanone ketoxime with this large particle diameter titanium molecular sieve catalysis cyclohexanone oxamidinating, catalysqt deactivation is very fast, the cyclohexanone conversion ratio only has 72.9% after 30 hours, take cyclohexanone oxime selectively as 93.2%.
DE19623611 discloses the employing Ludox and the HTS fine powder adds plasticizer again, prepares the method for large particle diameter HTS by extrusion.But the intensity of the catalyst that obtains is undesirable.
WO98/55229 discloses and has adopted Ludox and HTS fine powder to add water and pure mixture as bonding agent again, prepares the method for large particle diameter HTS by extrusion.But the intensity of the catalyst that obtains is also undesirable.
In sum, the particle diameter of the HTS of the existing method that prepare titanium-silicon molecular sieve catalyst of large particle diameter or preparation is little, and reaction is very difficult with separating of product afterwards; The bonding agent that perhaps adopts contains the component that causes easily hydrogen peroxide decomposes, and the hydrogen peroxide utilization rate is reduced; Perhaps its intensity is low, can't satisfy application requirements.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, provide a kind of reaction rear easily separation, do not contain the component that causes easily hydrogen peroxide decomposes, and the preparation method of the HTS microspherical catalyst that intensity is high, the life-span is long.
Technical scheme of the present invention is summarized as follows:
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 1%-6%, HTS and SiO 2Mass ratio be 1: 0.05~0.5;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 500 ℃~950 ℃ roastings 1~100 hour, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Described HTS and SiO 2Mass ratio be preferably 1: 0.06~0.3, preferably 1: 0.08~0.13.
The sintering temperature of described step (3) is preferably 550 ℃.
Advantage of the present invention: HTS exists with microspheres form, particle diameter is large, do not contain the component that causes easily hydrogen peroxide decomposes, can be used for the corresponding ketoxime of catalyzing ketone amidoxime preparation, catalyzing expoxidation of olefines prepares olefin epoxide, in the course of reaction, product and unreacted reactant, solvent are easy to separate with catalyst, and catalyst life is long.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.Embodiments of the invention are in order to enable those skilled in the art to understand better the present invention, but the present invention are not imposed any restrictions.
Silicate aqueous solution can adopt the preparation of various methods that oneself knows, what the present invention adopted is that the sodium metasilicate spent ion exchange resin carries out the cation exchange preparation, but experiment showed, with what other method prepared and also can be used for the present invention.
Mist projection granulating uses sponging granulator, inlet temperature 250-350 ℃, outlet temperature 120-180 ℃.
Embodiment 1
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 3%, HTS and SiO 2Mass ratio be 1: 0.12;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 550 ℃ of roastings 6 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 2
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 4%, HTS and SiO 2Mass ratio be 1: 0.08;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 500 ℃ of roastings 100 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 3
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 6%, HTS and SiO 2Mass ratio be 1: 0.13;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 950 ℃ of roastings 1 hour, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 4
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 1%, HTS and SiO 2Mass ratio be 1: 0.06;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 600 ℃ of roastings 20 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 5
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 2%, HTS and SiO 2Mass ratio be 1: 0.5;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 700 ℃ of roastings 15 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 6
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 2%, HTS and SiO 2Mass ratio be 1: 0.05;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 800 ℃ of roastings 10 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 7
A kind of preparation method of HTS microspherical catalyst is comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 2%, HTS and SiO 2Mass ratio be 1: 0.3;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 850 ℃ of roastings 2 hours, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
Embodiment 8
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 1 preparation prepares cyclohexanone oxime.Ammoximation reaction employing normal pressure is starched continuously the attitude reaction unit and is carried out.Reactor is three mouthfuls of glass reactors of 100mL, and the filter membrane that the aperture is 5 μ m is housed, and a side mouth is charging aperture, and the opposite side mouth is discharging opening.At first in reactor, add 3g HTS microspherical catalyst, the 80mL tert-butyl alcohol, after reaching reaction temperature, pass into ammonia, H 2O 2Mass content is that 30% the aqueous solution, tert-butyl alcohol mass content are that 85% the aqueous solution and cyclohexanone begin reaction, and wherein the mol ratio of ammonia and cyclohexanone is 2.5, H 2O 2With the mol ratio of cyclohexanone be 1.05, the mass ratio of water and the tert-butyl alcohol is 2.5, the time of staying of cyclohexanone in reactor is 70 minutes.Control reaction temperature at 73+1 ℃ with water bath with thermostatic control.Collect product from discharging opening after the reaction beginning, the product liquid that 1 accumulation of analysis in per 1 hour is collected.Product with Agilent 4890 gas chromatograph analyses, uses SE-54 capillary column, hydrogen flame detector analysis after centrifugation.Analysis condition is: 250 ℃ of vaporizer temperature, 270 ℃ of sensing chamber's temperature, N 2Be carrier gas, its flow 1.5mlmin -1, split ratio 70, temperature programming: 100 ℃ of initial temperature, stop 10min, then the speed with 15 ℃/min is warming up to 250 ℃, stops 15min.
The concentration of hydrogen peroxide is measured with Indirect Iodine Method.
The concentration of ammonia is that the reactant liquor that will contain ammonia is added in the excessive hydrochloric acid standard solution, with the hydrochloric acid of standard solution of sodium hydroxide overtitration, with methyl red or bromophenol indigo plant as indicator.
The conversion ratio X of cyclohexanone CYSelective S with cyclohexanone oxime CYOCalculate with following formula respectively:
X CY = n CY 0 - n CY n CY 0 × 100 %
S CYO = n CYO n CY 0 - n CY × 100 %
In the formula:
Figure BDA00002466786200043
The molal quantity of the initial cyclohexanone of-reaction; n CYThe molal quantity of cyclohexanone in the-product; n CYOThe molal quantity of cyclohexanone oxime in the-product.
The life-span of catalyst is defined as the cyclohexanone conversion ratio and obviously descends (more than at least 1%) front 1 hour accumulation reaction time.
Reaction result is listed in table 1.
Embodiment 9
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 2 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 10
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 3 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 11
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 4 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 12
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 5 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 13
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 6 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 14
HTS microspherical catalyst catalysis of pimelinketone oxamidine with embodiment 7 preparations prepares cyclohexanone oxime.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Embodiment 15
Titanium molecular sieve catalysis preparing cyclohexanone oxime by ammoximation of cyclohexanone with 0.1~0.3 μ m.Reaction condition is with embodiment 8.Reaction result is listed in table 1.
Table 1 HTS microspherical catalyst catalysis of pimelinketone oxamidine reaction result
Figure BDA00002466786200051
The result of table 1 shows, with the HTS microspherical catalyst catalysis of pimelinketone oxamidine reaction of method preparation of the present invention, the cyclohexanone conversion ratio is more than 97.8%, cyclohexanone oxime selectively more than 98.6%, the life-span of catalyst is more than 148 hours.But directly the HTS with 0.1~0.3 μ m is catalyst because particle diameter is smaller, in the course of reaction loss of catalyst very serious, cause the life-span of catalyst very short.

Claims (4)

1. the preparation method of a HTS microspherical catalyst is characterized in that being comprised of following steps:
(1) be that the HTS of 0.1~0.3 μ m and silicate aqueous solution stir and make slurries with particle diameter; SiO in the described silicate aqueous solution 2The quality percentage composition be 1%-6%, HTS and SiO 2Mass ratio be 1: 0.05~0.5;
(2) the slurries mist projection granulating with step (1) is prepared into microballoon;
(3) microballoon that step (2) is prepared was 500 ℃~950 ℃ roastings 1~100 hour, and obtaining particle diameter is the HTS microspherical catalyst of 5~80 μ m.
2. the preparation method of a kind of HTS microspherical catalyst according to claim 1 is characterized in that described HTS and SiO 2Mass ratio be 1: 0.06~0.3.
3. the preparation method of a kind of HTS microspherical catalyst according to claim 3 is characterized in that described HTS and SiO 2Mass ratio be 1: 0.08~0.13.
4. the preparation method of a kind of HTS microspherical catalyst according to claim 1, the sintering temperature that it is characterized in that described step (3) is 550 ℃.
CN2012104894409A 2012-11-26 2012-11-26 Preparation method of microspherical catalyst with titanium silicalite molecular sieve Pending CN102989502A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103212435A (en) * 2013-03-28 2013-07-24 华东师范大学 Preparation method of microsphere titanium silicalite molecular sieve catalyst
CN104368382A (en) * 2014-09-30 2015-02-25 中国天辰工程有限公司 Preparation method of titanium-silicon molecular sieve microballoon catalyst
CN104495868A (en) * 2014-11-28 2015-04-08 巨化集团技术中心 Preparation method of large-particle-size titanium silicon molecular sieve
CN104495867A (en) * 2014-11-28 2015-04-08 巨化集团技术中心 Preparation method of titanium-silicate molecular sieve having large particle size
CN105524022A (en) * 2015-11-27 2016-04-27 天津大学 Preparation method for epoxypropane
CN115557840A (en) * 2022-11-04 2023-01-03 浙江新化化工股份有限公司 Preparation method of 2-nitropropane and catalyst used in preparation method

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CN101480622A (en) * 2009-02-13 2009-07-15 中国天辰工程有限公司 Method for preparing titanium-silicon molecular sieve catalyst of large particle diameter
CN102145300A (en) * 2011-03-08 2011-08-10 华东师范大学 Microsphere TS-1 catalyst and preparation method of microsphere TS-1 catalyst
CN102614911A (en) * 2012-02-23 2012-08-01 湘潭大学 One-step molding method of titanium silicalite molecular sieve

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US6551546B1 (en) * 1998-04-08 2003-04-22 Basf Aktiengesellschaft Method for producing a shaped body using a metal oxide sol
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103212435A (en) * 2013-03-28 2013-07-24 华东师范大学 Preparation method of microsphere titanium silicalite molecular sieve catalyst
CN104368382A (en) * 2014-09-30 2015-02-25 中国天辰工程有限公司 Preparation method of titanium-silicon molecular sieve microballoon catalyst
CN104495868A (en) * 2014-11-28 2015-04-08 巨化集团技术中心 Preparation method of large-particle-size titanium silicon molecular sieve
CN104495867A (en) * 2014-11-28 2015-04-08 巨化集团技术中心 Preparation method of titanium-silicate molecular sieve having large particle size
CN105524022A (en) * 2015-11-27 2016-04-27 天津大学 Preparation method for epoxypropane
CN105524022B (en) * 2015-11-27 2018-01-02 天津大学 A kind of method for preparing expoxy propane
CN115557840A (en) * 2022-11-04 2023-01-03 浙江新化化工股份有限公司 Preparation method of 2-nitropropane and catalyst used in preparation method
CN115557840B (en) * 2022-11-04 2023-11-10 浙江新化化工股份有限公司 Preparation method of 2-nitropropane and catalyst used in preparation method

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