CN106582807A - Modified titanium-silicon molecular sieve, modification method and application thereof in propylene epoxidation reaction - Google Patents
Modified titanium-silicon molecular sieve, modification method and application thereof in propylene epoxidation reaction Download PDFInfo
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Abstract
The invention discloses a modified titanium-silicon molecular sieve, a modification method, and application thereof in propylene epoxidation reaction. The modified titanium-silicon molecular sieve is obtained by the following steps: dissolving barium salt in water to prepare a barium salt aqueous solution, and then adding a strip-shaped titanium-silicon molecular sieve, wherein the weight ratio of the barium salt to the water to the strip-shaped titanium-silicon molecular sieve is (0.001-0.5):(0.1-5):1; and performing impregnation for 1-72h, performing filtration, drying a solid at 80-120 DEG C for 3-5h, and then performing roasting at 500-550 DEG C for 4-12h to obtain the modified titanium-silicon molecular sieve, wherein the strip-shaped titanium-silicon molecular sieve is obtained by mixing titanium-silicon molecular sieve raw powder with sesbania cannabina powder and silica sol uniformly and then performing strip extrusion forming, and the barium salt is barium nitrate, barium acetate or barium chloride. The modified molecular sieve is a strip-shaped titanium-silicon molecular sieve with an MFI structure; and as a catalyst, the modified molecular sieve is applied to a liquid phase propylene epoxidation process. The modification method disclosed by the invention is simple in operation process, and due to a mutual synergistic effect between the barium salt and the titanium-silicon molecular sieve, the modification method, when applied to the propylene epoxidation reaction, can obviously reduce invalid decomposition of hydrogen peroxide as well as effectively improve the effective utilization of hydrogen peroxide and the selectivity of a product namely propylene epoxide.
Description
Technical field
The present invention relates to a kind of modifying titanium-silicon molecular sieve and its method of modifying, and further to modified molecular sieve in liquid phase
Application in propylene ring oxidation reaction, belongs to technical field of inorganic.
Background technology
Nineteen eighty-three Taramasso et al. is successfully incorporated into titanium in pure silica zeolites, and titanium-silicon molecular sieve TS-1 has been synthesized first.
Titanium-silicon molecular sieve TS-1 belongs to rhombic system, with ZSM-5 molecular sieve identical MFI topological structure.Due to transition metal
The introducing of titanium causes TS-1 to be provided with the catalytic oxidation performance of uniqueness.TS-1 is widely used in alkene epoxidation, the portion of alkane
In dividing the catalytic oxidations such as the hydroxylating of oxidation, oxidation of alcohols, the oximate of ketone, phenol and benzene.
Hydrogen peroxide is generally acknowledged Green Oxidant, and its oxidized byproduct only has water.Late 1970s are it is found that TS-1 can
Using the catalyst as propylene ring oxidation reaction, since then TS-1 has opened the sequence with hydrogen peroxide as oxidizer catalytic alkene epoxidation
Curtain.TS-1/H2O2System reaction condition is gentle, atom utilization is high, process safety, low in the pollution of the environment, process is simple, is one
Plant the green chemistry chemical technology new technology with broad prospect of application.
If the titanium-silicon molecular sieve TS-1 being synthesized using classical approach is not carried out follow-up process and is directly used in epoxidation of propylene
In course of reaction, then the shortcomings of can there is active low and poor selectivity of product, simultaneously because causing it the characteristics of TS-1 itself to double
Oxygen water itself has certain decomposability, and this undoubtedly reduces the effective rate of utilization of hydrogen peroxide in reaction, and decomposing hydrogen dioxide solution is produced
O2Can be present in response system, increased the danger of Chemical Manufacture.Therefore people constantly change anti-for epoxidation of propylene
The synthesis of the TS-1 for answering and method of modifying, to improve the reactivity of catalyst and the selectivity of product propene oxide.
At present, generally using organic base (as fatty amines, alcaminess, quaternary ammonium alkaloid compound, TPAOH, four
Ethyl ammonium hydroxide, n-propylamine, hexamethylene diamine), organic amine (diethylamine, triethylamine, Tetramethylammonium hydroxide, tetrabutyl hydrogen-oxygen
Change the aqueous solution such as ammonium), mineral acid (hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid), nitrate or acetate (copper, lead, cobalt, nickel,
The nitrate of silver etc. or the aqueous solution of acetate), soluble magnesium salt (such as magnesium sulfate, magnesium chloride), aluminum soluble salt (as aluminum chloride,
Aluminum sulfate, aluminum nitrate), noble metal (Ru, R, Pd, Re, Os, Ir, Pt, Au etc.), organic sequestering agent aqueous slkali (such as
1,2-diaminocyclohexane tetraacetic acid, hydroxyethylethylene diamine tri-acetic acid, ethylenediaminetetraacetic acid, citric acid, glutamic acid, tartaric acid etc.) etc. it is right
HTS is modified process.When but above-mentioned modifying agent is modified, carried out at 100～240 DEG C using crystallizing kettle,
There is certain requirement to equipment, need to bear certain pressure, processing procedure is loaded down with trivial details and processing cost is higher；Using precious metal salt
When being modified process, due to having used precious metal raw material, therefore processing cost is higher；Process is modified using mineral acid,
The equipment of being also required to has certain rotproofness, and the waste water for discharging is also required to neutralisation treatment.And above-mentioned method of modifying,
It is that molecular screen primary powder is modified, modified solid-liquid separation (especially to the separation of nano level molecular sieve) is extremely difficult.
The content of the invention
The technical problem to be solved is to be directed to the deficiencies in the prior art, and provides a kind of changing for HTS
Property method, without the need for special consersion unit, using the strip HTS after molding as modified object, solid-liquid separation operation letter
It is single；Using the aqueous solution of barium salt as modifying agent, modifying agent is cheap and easy to get, and mutually association occurs between barium salt and HTS
Same-action, so that the HTS for preparing significantly reduces the decomposition to hydrogen peroxide in propylene ring oxidation reaction, improves
The effective rate of utilization and the selectivity of product propene oxide of hydrogen peroxide.
The second object of the present invention is to provide a kind of HTS modified through above-mentioned method of modifying.
The third object of the present invention is to provide a kind of application of above-mentioned modified HTS during epoxidation of propylene.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of method of modifying of HTS, comprises the following steps：Barium salt is dissolved in into water to be prepared into after the aqueous solution of barium salt, plus
Enter strip HTS, 1～72h is impregnated under quiescent conditions, filter and remove after solution, solid is placed in baking oven at 80～120 DEG C
Under the conditions of dry 3～5h, be then placed in again in Muffle furnace after 4～12h of roasting under the conditions of 500～550 DEG C, obtain final product Barium monoxide be modified
HTS.
In above-mentioned technical proposal, described strip HTS is that HTS original powder prepared by traditional handicraft is mixed with field mountain valley with clumps of trees and bamboo powder
After closing uniformly, extruded moulding after the further mix homogeneously of Ludox is added, concretely comprised the following steps：Take 20 grams of HTSs original powder with
After 1 gram of field mountain valley with clumps of trees and bamboo powder mix homogeneously, add 14 milliliters of 30wt% the further mix homogeneously of Ludox after, with banded extruder extrusion into
Type, is finally dried the sample of molding 12 hours under the conditions of 100 DEG C, and then roasting 6 hours under the conditions of 550 DEG C, obtain
Strip HTS with MFI structure.
In above-mentioned technical proposal, the weight ratio of described barium salt, water and strip HTS is 0.001～0.5:0.1～5:1.
Preferably, the weight ratio of described barium salt, water and strip HTS is 0.001～0.1:0.1～2:1.
In above-mentioned technical proposal, described barium salt is soluble barium salt, such as any one in barium nitrate, barium acetate, barium chloride
Kind.
Preferably, described barium salt is barium nitrate or barium acetate.
In above-mentioned technical proposal, described dip time is preferably 12～48h.
In above-mentioned technical proposal, the step such as described dipping, drying, roasting can be repeated one or more times to strip titanium silicon molecule
Sieve is modified.
The present invention also provides a kind of HTS being modified through above-mentioned method of modifying, and the molecular sieve is the bar with MFI structure
Shape HTS.
The present invention also provides a kind of HTS answering in liquid propylene epoxidation process being modified through above-mentioned method of modifying
With with methanol as solvent, concrete reaction condition is described epoxidation of propylene process：2.5～3.0Mpa of reaction pressure, reaction
35～40 DEG C of temperature, propylene 0.8～1.2h of air speed-1, propylene and H2O2Mol ratio is 2:1～4:1.
The advantage of technical solution of the present invention is, the strip HTS after modified pair as if molding, solid-liquid separation operation is non-
It is often simple；Using barium salt molecular sieve is modified as modifying agent, due to barium salt and the mutual synergism of HTS, is made
Obtaining modified molecular sieve can significantly reduce the decomposition of hydrogen peroxide in propylene ring oxidation reaction, effectively improve hydrogen peroxide
Effectively utilizes and product propene oxide selectivity.
Specific embodiment
The specific embodiment of technical solution of the present invention is described in detail below, but the present invention is not limited to description below：
Various reagents used in the embodiment of the present invention are commercially available chemical reagent.
Described in the embodiment of the present invention and comparative example HTS original powder be traditionally " Zeolites,
Page 1992, Vol.12 the 943rd～950 " described by method be prepared, specially：With tetraethyl orthosilicate as silicon source, metatitanic acid
Four butyl esters are titanium source, and TPAOH is template, in 150～200 DEG C of crystallization 12～48 hours, Jing was filtered, washing,
HTS original powder is obtained after dry, roasting.
Comparative example：Prepare strip HTS
The 20g HTS original powder that traditionally prepared by method and 1 gram of field mountain valley with clumps of trees and bamboo powder are taken, 14 millis are added after mix homogeneously
The further mix homogeneously of Ludox of 30wt% is risen, banded extruder extruded moulding is then used, finally by the sample of molding in 100 DEG C of bars
It is dried 12 hours under part, then roasting 6 hours under the conditions of 550 DEG C, obtain strip HTS, are labeled as TS-1.
Embodiment 1：Strip HTS is modified
0.34g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 24h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-A,
Jing is determined, and the mass fraction of BaO is 0.22% in TS-1-A.
Embodiment 2：
0.34g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 48h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-B,
Jing is determined, and the mass fraction of BaO is 0.24% in TS-1-B.
Embodiment 3：
0.68g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 36h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-C,
Jing is determined, and the mass fraction of BaO is 0.49% in TS-1-C.
Embodiment 4：
1.36g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 24h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-D,
Jing is determined, and the mass fraction of BaO is 0.95% in TS-1-D.
Embodiment 5：
2.72g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 48h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-E,
Jing is determined, and the mass fraction of BaO is 2.1% in TS-1-E.
Embodiment 6：
6.8g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast enforcements to be prepared from
TS-1, impregnate 24h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4h under the conditions of 100 DEG C,
Then it is placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-F, Jing
Determine, the mass fraction of BaO is 4.9% in TS-1-F.
Embodiment 7：
9.52g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 36h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-G,
Jing is determined, and the mass fraction of BaO is 6.1% in TS-1-G.
Embodiment 8：
13.6g barium nitrates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 24h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-H,
Jing is determined, and the mass fraction of BaO is 8.3% in TS-1-H.
Embodiment 9：
1.33g barium acetates are dissolved in 30g deionized waters and are prepared into after the aqueous solution of barium salt, add 30g contrast implement prepare and
Into TS-1, impregnate 48h under quiescent conditions, filter and remove after solution, solid is placed in baking oven and dries 4 under the conditions of 100 DEG C
H, is then placed in again in Muffle furnace after roasting 6h under the conditions of 550 DEG C, obtains modified HTS, is labeled as TS-1-I,
Jing is determined, and the mass fraction of BaO is 0.97% in TS-1-C.
Application examples：
HTS prepared by the embodiment of the present invention and comparative example, is applied to epoxidation of propylene fixed bed anti-as catalyst
During answering, catalyst sample is placed in rustless steel jacketed reaction pipe, the two ends of reaction tube are carried out with the inert ceramic balls of φ 3mm
Filling.In course of reaction, it is 3.0Mpa that nitrogen maintains system pressure, and it is 38 DEG C to keep reaction temperature with thermostatic water-circulator bath,
Reactant hydrogen peroxide and propylene and solvent methanol feed simultaneously, propylene air speed 0.8h-1, propylene and H2O2Mol ratio is 3；Instead
Product analysis are regularly carried out during answering, indicator reaction is H2O2Conversion ratio (XH2O2) and effective rate of utilization (UH2O2), and
Expoxy propane selectivity (SPO)。
Strip HTS and modified with 1～9 pair of strip HTS of the embodiment of the present invention obtain prepared by comparative example
Result of the molecular sieve in propylene ring oxidation reaction it is as shown in table 1：
Table 1：Result of the different HTSs in propylene ring oxidation reaction
| Catalyst is numbered | XH2O2(%) | SPO(%) | UH2O2(%) |
| TS-1 | 98.2 | 88.2 | 80.1 |
| TS-1-A | 97.7 | 92.5 | 83.7 |
| TS-1-B | 98.1 | 92.3 | 84.0 |
| TS-1-C | 97.9 | 94.6 | 88.2 |
| TS-1-D | 98.1 | 97.8 | 95.5 |
| TS-1-E | 97.6 | 97.0 | 94.7 |
| TS-1-F | 97.2 | 97.6 | 94.2 |
| TS-1-G | 97.8 | 98.2 | 94.4 |
| TS-1-H | 95.8 | 98.4 | 93.8 |
| TS-1-I | 98.4 | 97.9 | 95.3 |
As can be seen from the above table, process is modified to HTS using barium salt, propylene ring oxidation reaction can be significantly improved
During H2O2Effective rate of utilization, and product propene oxide selectivity is also with increasing, but when in modified HTS
Barium monoxide content is improved to after more than 1%, H2O2Effective rate of utilization no longer improve.
Examples detailed above is technology design to illustrate the invention and technical characterstic, can not limit protection model of the invention with this
Enclose.Equivalent transformation or modification that all essence of the invention is done, all should be included within the scope of the present invention.
Claims (10)
1. a kind of method of modifying of HTS, comprises the following steps：Barium salt is dissolved in into water to be prepared into after the aqueous solution of barium salt,
Strip HTS is added, 1～72h is impregnated under quiescent conditions, filtered and remove after solution, solid is placed in baking oven
3～5h is dried under the conditions of 80～120 DEG C, is then placed in again in Muffle furnace after 4～12h of roasting under the conditions of 500～550 DEG C, obtain final product oxygen
Change the modified HTS of barium.
2. method according to claim 1, it is characterised in that described strip HTS is by following method systems
Standby：Take after the field mountain valley with clumps of trees and bamboo powder of HTS original powder prepared by 20 grams of traditional handicrafts with 1 gram mixs homogeneously, add 14 in the least
After rising the further mix homogeneously of Ludox of 30wt%, banded extruder extruded moulding is used, finally by the sample of molding in 100 DEG C of conditions
Lower drying 12 hours, then roasting obtains described strip HTS after 6 hours under the conditions of 550 DEG C.
3. method according to claim 1, it is characterised in that the weight of described barium salt, water and strip HTS
Than for 0.001～0.5:0.1～5:1；Described water is deionized water.
4. method according to claim 3, it is characterised in that the weight of described barium salt, water and strip HTS
Than for 0.001～0.1:0.1～2:1.
5. method according to claim 1, it is characterised in that described barium salt is soluble barium salt such as barium nitrate, acetic acid
Any one in barium, barium chloride.
6. method according to claim 5, it is characterised in that described barium salt is barium nitrate or barium acetate.
7. method according to claim 1, it is characterised in that described dip time is 12～48h.
8. method according to claim 1, it is characterised in that described dipping, drying, calcination stepses can repeat
It is secondary or repeatedly strip HTS is modified.
9. a kind of HTS modified through the method described in any one of claim 1～8, it is characterised in that described
Molecular sieve is the strip HTS with MFI structure.
10. application of the HTS described in a kind of claim 9 as catalyst in liquid propylene epoxidation process, its
It is characterised by, with methanol as solvent, reaction condition is described epoxidation of propylene process：2.5～3.0Mpa of reaction pressure, instead
Answer 35～40 DEG C of temperature, propylene 0.8～1.2h of air speed-1, propylene and H2O2Mol ratio is 2:1～4:1.
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| CN105854933A (en) * | 2016-06-21 | 2016-08-17 | 中触媒新材料股份有限公司 | Modified titanium-silicon molecular sieve as well as modification method 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 |
| CN110252394A (en) * | 2019-07-18 | 2019-09-20 | 北京赛诺时飞石化科技有限公司 | A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation |
| CN112808306A (en) * | 2021-01-13 | 2021-05-18 | 华东理工大学 | Preparation method and application of metal oxygen cluster catalyst with stable organic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105854933A (en) * | 2016-06-21 | 2016-08-17 | 中触媒新材料股份有限公司 | Modified titanium-silicon molecular sieve as well as modification method and application thereof |
| CN105854933B (en) * | 2016-06-21 | 2018-08-14 | 中触媒新材料股份有限公司 | A kind of modifying titanium-silicon molecular sieve and its method of modifying and application |
| 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 |
| CN110252394A (en) * | 2019-07-18 | 2019-09-20 | 北京赛诺时飞石化科技有限公司 | A kind of catalyst and its preparation, application preparing propylene oxide for propylene oxidation |
| CN112808306A (en) * | 2021-01-13 | 2021-05-18 | 华东理工大学 | Preparation method and application of metal oxygen cluster catalyst with stable organic acid |
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Effective date of registration: 20190418 Address after: 274500 Dongming County Chemical Park in Heze, Shandong Patentee after: Zhonghai environmental protection material Co Ltd Address before: 116023 Liaoning Dalian pun Wan New Area Pine Island Chemical Industrial Park Patentee before: DALIAN HETEROGENEOUS CATALYST CO., LTD. |