CN106115732A - A kind of modifying titanium-silicon molecular sieve and method of modifying thereof and application - Google Patents
A kind of modifying titanium-silicon molecular sieve and method of modifying thereof and application Download PDFInfo
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- CN106115732A CN106115732A CN201610443772.1A CN201610443772A CN106115732A CN 106115732 A CN106115732 A CN 106115732A CN 201610443772 A CN201610443772 A CN 201610443772A CN 106115732 A CN106115732 A CN 106115732A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention discloses a kind of modifying titanium-silicon molecular sieve and method of modifying thereof and application, first nitrate and water mix homogeneously are prepared as nitrate aqueous solution, then by HTS powder infusion in nitrate aqueous solution, filter after dipping 12～96h, after the solid obtained is dried at 90～120 DEG C, at 450～550 DEG C after roasting 5～14h, obtain modifying titanium-silicon molecular sieve.The framing structure of modifying titanium-silicon molecular sieve is without substantially changing, but the mutual synergism due to metal-oxide Yu HTS, make it can significantly reduce the decomposition of hydrogen peroxide in propylene ring oxidation reaction, can effectively improve the effective rate of utilization of hydrogen peroxide.Modifying titanium-silicon molecular sieve, in the liquid propylene epoxidation reaction with acetonitrile as solvent, reduces the decomposition to hydrogen peroxide, to improve the effective rate of utilization of its hydrogen peroxide in propylene ring oxidation reaction.
Description
Technical field
The present invention relates to the method for modifying of a kind of HTS, it is molten that modified HTS can be used for acetonitrile
In the liquid propylene epoxidation reaction of agent, belong to technical field of inorganic.
Background technology
In recent years, MWW type HTS, by the structural advantage of its uniqueness, is taken the course of its own, and increasingly becomes research heat
Point, becomes antagonism synthetic technology and main forces of the application technology quite TS-1 molecular sieve of maturation.From synthetic method and used
Raw material compare, synthesis template used by MWW structure titanium silicon molecular sieve and other material cost are cheap, and synthetic method is the most multiple
Various, the most important is MWW type HTS duct demonstrates stronger plasticity and higher compared with TS-1 molecular sieve
Catalysis activity.
HTS is as a kind of novel green catalyst, in HTS/hydrogen peroxide heterogeneous catalytic system
Providing a kind of eco-friendly green approach for organic epoxidation reaction, it uses hydrogen peroxide to be oxygen source, will not degree of depth oxygen
Changing, reaction condition is gentle, has high activity, high selectivity, and product is easily separated, advantage, and the hydrogen peroxide reaction such as can be recycled
After product be water, environmentally safe, therefore in terms of catalytic organism oxidation, there is unique advantage.MWW type titanium silicon is divided
For son sieve and the catalytic performance of both TS-1 molecular sieves, in methanol is solvent, TS-1 catalyst can effectively be catalyzed with
Hydrogen peroxide is the oxidation reaction of oxidant, but inevitably causes the solvolytic reaction of product and methanol, causes reaction choosing
Selecting property is relatively low, and MWW type HTS is without with methanol as solvent, and acetonitrile elected as by its solvent more, and reaction selectivity is higher.
The MWW type HTS of traditional handicraft synthesis has the existence of more extra-framework titanium, causes its catalysis to be lived
Property relatively low, reactant is had stronger decomposition, so it need to be modified, improve its catalysis activity and to double
The effective rate of utilization of oxygen water.
Summary of the invention
The technical problem to be solved is for the deficiencies in the prior art, and provides a kind of titanium silicon molecule
The method of modifying of sieve, is modified it by metal salt solution Ti-MWW molecular sieve, and operation is simple, and process is easily controlled
System.
The two of the purpose of the present invention are to provide a kind of through the modified modifying titanium-silicon molecular sieve obtained of said method, modified
The framing structure of HTS is without substantially changing, but due to the mutual synergism of metal-oxide Yu HTS, makes
It can significantly reduce the decomposition of hydrogen peroxide in propylene ring oxidation reaction, can effectively improve the effective of hydrogen peroxide
Utilization rate.
The three of the purpose of the present invention are to provide the application of a kind of above-mentioned modifying titanium-silicon molecular sieve, are used for acetonitrile as solvent
In liquid propylene epoxidation reaction, reduce the decomposition to hydrogen peroxide, to improve its hydrogen peroxide in propylene ring oxidation reaction
Effective rate of utilization.
To achieve these goals, the present invention adopts the following technical scheme that
The method of modifying of a kind of HTS, comprises the following steps:
First nitrate and water mix homogeneously are prepared as nitrate aqueous solution, then HTS be impregnated in nitrate
In aqueous solution, filter after dipping 12～96h, after the solid obtained dries 2-6h at 90～120 DEG C, at 450～550 DEG C
After roasting 5～14h, obtain modifying titanium-silicon molecular sieve；
The mass ratio of described nitrate, water and si molecular sieves is: 0.003～0.5:0.5～5:1.
In technique scheme, described nitrate is barium nitrate, or, barium nitrate mixes with zinc nitrate and/or Lanthanum (III) nitrate
The mixture closed, barium nitrate, zinc nitrate, the mass ratio of Lanthanum (III) nitrate are 1:0～3.5:0～3.0；
Further, described barium nitrate, zinc nitrate, the mass ratio of Lanthanum (III) nitrate are preferably 1:0.5～3.5:0.5～3.0,
More preferably 1:1.0～2.0:0.8～2.0.
In technique scheme, the mass ratio of described nitrate, water and HTS is preferably: 0.003～0.1:1
～2:1.
In technique scheme, described dip time is preferably 36～72h.
In technique scheme, described HTS be conventionally " J.Phys.Chem.B, 105 (2001)
289；J.Catal., method disclosed in 202 (2001) 24 " is prepared from, and method comprises the following steps: with alkaline silica sol be
Silicon source, butyl titanate is titanium source, and boric acid is crystallization in motion agent, and piperidines is directed agents, 170 DEG C of crystallization 3-10d, through filtering, washing
Wash, be dried, obtain HTS after roasting；Described alkaline silica sol, butyl titanate, boric acid, the mass ratio of piperidines are
1:0.02～0.05:0.2～0.6:0.5～0.8.
The present invention also provides for a kind of modifying titanium-silicon molecular sieve, is obtained, this modification by the modification of above-mentioned method of modifying
HTS has MWW structure, and XRD spectra is as shown in Figure 1.
The present invention also provides for the application of a kind of above-mentioned modifying titanium-silicon molecular sieve, is used for acetonitrile as solvent as catalyst
In liquid propylene epoxidation reaction, this reaction is carried out in fixed-bed reactor, and reaction condition is: temperature 35～40 DEG C, pressure
Power 2.5～3.0Mpa, the air speed 0.8～1.2h-1 of propylene, propylene and H2O2Mol ratio be 2～4:1.
The advantage of technical solution of the present invention is: HTS method of modifying of the present invention, and operation is simple,
Simultaneously because metal-oxide and the mutual synergism of HTS so that it is can be obvious in liquid propylene epoxidation reaction
The decomposition reducing hydrogen peroxide, it is possible to the effective effective rate of utilization improving hydrogen peroxide.
Accompanying drawing explanation
The XRD spectra of modifying titanium-silicon molecular sieve prepared by Fig. 1: the embodiment of the present invention.
Detailed description of the invention
Hereinafter the detailed description of the invention of technical solution of the present invention is described in detail, but the present invention is not limited in following description
Holding, the reagent used in embodiment is commercially available chemically pure reagent.
In following example use HTS be conventionally " J.Phys.Chem.B, 105 (2001)
289；J.Catal., method disclosed in 202 (2001) 24 " is prepared from, and with alkaline silica sol for silicon source, butyl titanate is
Titanium source, boric acid is crystallization in motion agent, and piperidines is directed agents, described alkaline silica sol, butyl titanate, boric acid, the quality of piperidines
Ratio is 1:0.036:0.0414:0.608；Said components, 170 DEG C of crystallization 7d, obtains titanium through filtering, wash, being dried, after roasting
Si molecular sieves, this HTS is labeled as " comparison HTS ".
Embodiment 1:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: 1.2 grams of barium nitrates are dissolved in 60 grams go from
In sub-water, mix homogeneously is prepared as nitrate aqueous solution, impregnated in nitrate aqueous solution by 40 grams of comparison HTSs, leaching
Filtering after stain 36h, solid is dried after 5 hours then at 550 DEG C of roastings 8 hours at 110 DEG C, obtains modifying titanium-silicon molecular sieve, mark
Being designated as modifying titanium-silicon molecular sieve A, XRF measures 0.54% that the content of BaO in this molecular sieve is comparison HTS quality；Should
Modifying titanium-silicon molecular sieve has MWW structure, and XRD spectra is shown in Fig. 1.
Embodiment 2:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates and 2.16 gram of six water
Conjunction zinc nitrate is dissolved in mix homogeneously in 60 grams of deionized waters and is prepared as nitrate aqueous solution, by 40 grams of comparison HTSs dippings
In nitrate aqueous solution, filtering after dipping 36h, solid is dried after 5 hours then at 550 DEG C of roastings 8 hours at 110 DEG C,
To modifying titanium-silicon molecular sieve, being labeled as modifying titanium-silicon molecular sieve B, it is the most right that XRF measures the content of BaO, ZnO in this molecular sieve
According to HTS quality 0.38%, 0.57%.
Embodiment 3:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates and 1.76 gram of six water
Conjunction Lanthanum (III) nitrate is dissolved in mix homogeneously in 60 grams of deionized waters and is prepared as nitrate aqueous solution, by 40 grams of comparison HTSs dippings
In nitrate aqueous solution, filtering after dipping 36h, solid is dried after 5 hours then at 550 DEG C of roastings 8 hours at 110 DEG C,
To modifying titanium-silicon molecular sieve, being labeled as modifying titanium-silicon molecular sieve C, XRF measures BaO, La in this molecular sieve2O3Content be respectively
Comparison the 0.40% of HTS quality, 0.77%.
Embodiment 4:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates and 1.64 gram of six water
Conjunction zinc nitrate is dissolved in mix homogeneously in 60 grams of deionized waters and is prepared as nitrate aqueous solution, by 40 grams of comparison HTSs dippings
In nitrate aqueous solution, filtering after dipping 36h, solid is dried after 5 hours then at 550 DEG C of roastings 8 hours at 110 DEG C,
To modifying titanium-silicon molecular sieve, being labeled as modifying titanium-silicon molecular sieve D, it is the most right that XRF measures the content of BaO, ZnO in this molecular sieve
According to HTS quality 0.45%, 0.42%.
Embodiment 5:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates and 1.24 gram of six water
Conjunction Lanthanum (III) nitrate is dissolved in mix homogeneously in 60 grams of deionized waters and is prepared as nitrate aqueous solution, by 40 grams of comparison HTSs dippings
In nitrate aqueous solution, filtering after dipping 36h, solid is dried after 5 hours then at 550 DEG C of roastings 8 hours at 110 DEG C,
To modifying titanium-silicon molecular sieve, being labeled as modifying titanium-silicon molecular sieve E, XRF measures BaO, La in this molecular sieve2O3Content be respectively
Comparison the 0.42% of HTS quality, 0.41%.
Embodiment 6:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates, 2.16 gram of six water
Close zinc nitrate and 1.76 grams of lanthanum nitrate hexahydrates are dissolved in mix homogeneously in 60 grams of deionized waters and are prepared as nitrate aqueous solution, by 40
Gram comparison HTS impregnated in nitrate aqueous solution, filters after dipping 36h, and solid is dried after 5 hours again at 110 DEG C
In 550 DEG C of roastings 8 hours, obtaining modifying titanium-silicon molecular sieve, be labeled as modifying titanium-silicon molecular sieve F, XRF measures in this molecular sieve
BaO、ZnO、La2O3Content be respectively comparison the 0.35% of HTS quality, 0.46%, 0.63%.
Embodiment 7:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates, 1.64 gram of six water
Close zinc nitrate and 1.24 grams of lanthanum nitrate hexahydrates are dissolved in mix homogeneously in 60 grams of deionized waters and are prepared as nitrate aqueous solution, by 40
Gram comparison HTS impregnated in nitrate aqueous solution, filters after dipping 36h, and solid is dried after 5 hours again at 110 DEG C
In 550 DEG C of roastings 8 hours, obtaining modifying titanium-silicon molecular sieve, be labeled as modifying titanium-silicon molecular sieve G, XRF measures in this molecular sieve
BaO、ZnO、La2O3Content be respectively comparison the 0.44% of HTS quality, 0.37%, 0.45%.
Embodiment 8:
A kind of modifying titanium-silicon molecular sieve, is prepared from by following method: by 1.2 grams of barium nitrates, 2.95 gram of six water
Close zinc nitrate and 2.08 grams of lanthanum nitrate hexahydrates are dissolved in mix homogeneously in 60 grams of deionized waters and are prepared as nitrate aqueous solution, by 40
Gram comparison HTS impregnated in nitrate aqueous solution, filters after dipping 36h, and solid is dried after 5 hours again at 110 DEG C
In 550 DEG C of roastings 8 hours, obtaining modifying titanium-silicon molecular sieve, be labeled as modifying titanium-silicon molecular sieve H, XRF measures in this molecular sieve
BaO、ZnO、La2O3Content be respectively comparison the 0.48% of HTS quality, 0.23%, 0.17%.
Application Example:
The modifying titanium-silicon molecular sieve that comparison HTS and embodiment 1-8 obtain is carried out experimental evaluation: first will urge
Agent through tabletting, sieving obtains 20-40 mesh catalyst, respectively 5 grams of catalyst samples are loaded on upper and lower two ends quartz sand and fill
Rustless steel chuck reaction tube in, in course of reaction, maintenance reaction pressure is 2.5Mpa, and reaction temperature is 40 DEG C, reactant
Hydrogen peroxide, propylene liguid and solvent acetonitrile are simultaneously in reaction tube by pump, and the air speed of propylene is 0.7h-1, propylene is with double
The mol ratio of oxygen water is 3.5:1, timing sampling analysis in course of reaction, and result is as shown in table 1, wherein, and XH2O2、SPO、UH2O2
Represent H respectively2O2Conversion ratio, expoxy propane selectivity and H2O2Effective rate of utilization.
Table 1: the catalytic effect in liquid propylene epoxidation reaction of different HTSs
| Sample source | Catalyst is numbered | XH2O2(%) | SPO(%) | UH2O2(%) |
| Comparison HTS | 98.5 | 98.6 | 82.3 | |
| Embodiment 1 | Modifying titanium-silicon molecular sieve A | 98.2 | 98.1 | 88.7 |
| Embodiment 2 | Modifying titanium-silicon molecular sieve B | 97.9 | 98.7 | 92.2 |
| Embodiment 3 | Modifying titanium-silicon molecular sieve C | 98.0 | 99.2 | 90.6 |
| Embodiment 4 | Modifying titanium-silicon molecular sieve D | 97.5 | 97.6 | 91.1 |
| Embodiment 5 | Modifying titanium-silicon molecular sieve E | 98.2 | 98.1 | 89.2 |
| Embodiment 6 | Modifying titanium-silicon molecular sieve F | 96.8 | 99.3 | 91.8 |
| Embodiment 7 | Modifying titanium-silicon molecular sieve G | 98.1 | 98.8 | 96.1 |
| Embodiment 8 | Modifying titanium-silicon molecular sieve H | 98.3 | 98.2 | 93.8 |
As can be seen from the above table, jointly act on obtained modified titanium silicon by Barium monoxide, zinc oxide and lanthana to divide
Son sieve, it can significantly improve H in course of reaction in liquid propylene epoxidation reaction2O2Effective rate of utilization.
Examples detailed above simply for technology design and the technical characterstic of the present invention are described, can not limit the present invention's with this
Protection domain.All equivalent transformations done according to the essence of the present invention or modification, all should contain in protection scope of the present invention
Within.
Claims (9)
1. the method for modifying of a HTS, it is characterised in that comprise the following steps:
First nitrate and water mix homogeneously are prepared as nitrate aqueous solution, then by HTS powder infusion in nitrate
In aqueous solution, filter after dipping 12～96h, after the solid obtained dries 2-6h at 90～120 DEG C, at 450～550 DEG C
After roasting 5～14h, obtain modifying titanium-silicon molecular sieve；
The mass ratio of described nitrate, water and HTS is: 0.003～0.5:0.5～5:1.
Method the most according to claim 1, it is characterised in that described nitrate is barium nitrate, or barium nitrate and nitric acid
The mixture that zinc and/or Lanthanum (III) nitrate mix, barium nitrate, zinc nitrate, the mass ratio of Lanthanum (III) nitrate are 1:0～3.5:0～3.0.
Method the most according to claim 2, it is characterised in that described barium nitrate, zinc nitrate, the mass ratio 1 of Lanthanum (III) nitrate:
0.5～3.5:0.5～3.0.
Method the most according to claim 3, it is characterised in that described barium nitrate, zinc nitrate, Lanthanum (III) nitrate mass ratio excellent
Elect 1:1.0～2.0:0.8～2.0 as.
Method the most according to claim 1, it is characterised in that the mass ratio of described nitrate, water and HTS
For: 0.003～0.1:1～2:1.
Method the most according to claim 1, it is characterised in that described dip time is 36～72h.
Method the most according to claim 1, it is characterised in that HTS is prepared from by the following method:
With alkaline silica sol for silicon source, butyl titanate is titanium source, and boric acid is crystallization in motion agent, and piperidines is directed agents, 170 DEG C of crystallization 3-
10d, obtains HTS through filtering, wash, being dried, after roasting；Described alkaline silica sol, butyl titanate, boric acid, piperazine
The mass ratio of pyridine is 1:0.02～0.05:0.2～0.6:0.5～0.8.
8. a modifying titanium-silicon molecular sieve, it is characterised in that be modified by method of modifying described in any one of claim 1～7
And obtain.
9. the application of the modifying titanium-silicon molecular sieve described in a claim 8, it is characterised in that as catalyst for acetonitrile
For in the liquid propylene epoxidation reaction of solvent, this reaction is carried out in fixed-bed reactor, and reaction condition is: temperature 35～
40 DEG C, pressure 2.5～3.0Mpa, the air speed 0.8～1.2h-1 of propylene, propylene and H2O2Mol ratio be 2～4:1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999124A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application |
| CN107999125A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW system with molecular sieve for preparing containing micropore-mesopore is standby and applies |
| CN109999903A (en) * | 2019-04-26 | 2019-07-12 | 中触媒新材料股份有限公司 | A kind of catalyst and preparation method thereof synthesizing acetonitrile |
| WO2021123214A1 (en) | 2019-12-20 | 2021-06-24 | Basf Se | A molding comprising a ti-mww zeolite and having a specific lewis acidity |
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| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
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| CN1555923A (en) * | 2004-01-10 | 2004-12-22 | 大连理工大学 | Modification method of titanium silicone molecular sieve and its application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107999124A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application |
| CN107999125A (en) * | 2017-12-14 | 2018-05-08 | 中触媒新材料股份有限公司 | A kind of core shell structure Ti-MWW system with molecular sieve for preparing containing micropore-mesopore is standby and applies |
| CN107999125B (en) * | 2017-12-14 | 2020-09-08 | 中触媒新材料股份有限公司 | Preparation and application of microporous-mesoporous-containing Ti-MWW molecular sieve with core-shell structure |
| CN107999124B (en) * | 2017-12-14 | 2020-11-24 | 中触媒新材料股份有限公司 | Core-shell structure Ti-MWW @ Si molecular sieve and preparation and application thereof |
| CN109999903A (en) * | 2019-04-26 | 2019-07-12 | 中触媒新材料股份有限公司 | A kind of catalyst and preparation method thereof synthesizing acetonitrile |
| WO2021123214A1 (en) | 2019-12-20 | 2021-06-24 | Basf Se | A molding comprising a ti-mww zeolite and having a specific lewis acidity |
| CN115066297A (en) * | 2019-12-20 | 2022-09-16 | 巴斯夫欧洲公司 | Moulded article comprising a Ti-MWW zeolite and having specific Lewis acidity |
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