CN104291352A - Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation - Google Patents

Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation Download PDF

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CN104291352A
CN104291352A CN201410514259.8A CN201410514259A CN104291352A CN 104291352 A CN104291352 A CN 104291352A CN 201410514259 A CN201410514259 A CN 201410514259A CN 104291352 A CN104291352 A CN 104291352A
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molecular sieve
titanium
modifying
sieve catalyst
silicon
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朱明乔
葛倩
卢建国
周云
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data

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Abstract

The invention discloses a method for preparing and modifying a titanium silicalite molecular sieve catalyst and application of the titanium silicalite molecular sieve catalyst in ketone oximation. The method comprises the following steps: (1) adding seed crystal into a titanium source, a silicon source, a first template agent, a first alkali source, water and additive which serve as raw materials to prepare a titanium silicalite molecular sieve A by adopting a hydrothermal synthesis method; (2) modifying the titanium silicalite molecular sieve A by using an acidic mixed solution to obtain a molecular sieve B; (3) modifying the molecular sieve B by using a second template agent and a second alkali source or mixed liquid of the second template agent and ammonium salt to obtain a molecular sieve C. The titanium silicalite molecular sieve catalyst prepared by the method can be applied to ketone oximation. According to the method, the synthesis cost of the titanium silicalite molecular sieve can be reduced, non-framework titanium in the molecular sieve can be effectively removed, and the catalyzing performance of the molecular sieve synthesized by a low-price system in a ketone oximation reaction can be remarkably improved.

Description

The preparation of titanium-silicon molecular sieve catalyst and method of modifying and the application in ketoxime
Technical field
The invention belongs to inorganic chemical synthesis technical field, relate in particular to a kind of preparation method in ketone oxamidinating with high performance titanium-silicon molecular sieve catalyst.
Background technology
HTS is the novel hetero-atom molecular-sieve of one of early 1980s exploitation, has regular orderly pore passage structure and larger pore volume and specific surface area.Under mild reaction conditions, HTS is with H 2o 2the aqueous solution is show unique selective oxidation catalytic performance in the oxidation reaction process of a series of organic compound of oxygenant.20th century the mid-80, Italian Montedipe company is first with pimelinketone, ammonia and H 2o 2for raw material, optionally cyclohexanone-oxime is generated through TS-1 katalysis under normal pressure, low temperature, this novel process is owing to having reaction conversion ratio and selectivity is high, process is pollution-free, without advantages such as producing ammonium sulfate byproducts, be subject to the attention of investigators, become a kind of novel method with the production cyclohexanone-oxime of wide application prospect.
Although better with the TS-1 reactivity worth of classical way synthesis, the template TPAOH (TPAOH) used due to it is expensive, and is unfavorable for its industrial applications.Follow-up study person uses relatively inexpensive 4-propyl bromide (TPABr) to replace expensive TPAOH to be template, and successfully synthesizes TS-1, but the TS-1 that its catalytic performance for Ammoximation reaction and classical approach synthesize exists larger gap.In order to improve the catalytic performance of the TS-1 of cheap method synthesis, numerous scholar is studied from catalyzer post-modification angle.
Investigators by updating template, titanium source, silicon source, alkali source and crystallization condition, the distinct TS-1 that used different synthetic methods to synthesize.Patent application US8772194 then there is provided a kind of method of synthesizing macrobead HTS, flocculation agent and peptizer mainly join in the molecular sieve crystal dispersion liquid prepared to form aggregated particles solution by the method, this solution is heat-treated after mixing with pre-synthesis colloidal sol, the HTS that final synthesis median size is greater than 5 μm.
Patent application CN101591024 discloses a kind of fluorochemicals, acid and water mixed solution of adopting to carry out the method for modification to molecular sieve, can extra-framework titanium species effectively in selectively removing HTS, the hydrophilic and hydrophobic of molecular sieve surface can be changed simultaneously, thus its catalytic oxidation performance is increased considerably.But because the fluorochemicals used in modifying process can cause environmental pollution to a certain degree, thus its application is subject to larger restriction.Patent application CN103214001 discloses a kind of preparation method of titanium silicalite molecular sieve catalyst with high performance, after adopting hydrothermal crystallization method synthesizing micron-grade HTS, use basic solution process, prepare titaniferous source again, the titaniferous modification liquid of organic formwork agent and alkali source carries out modification to it, finally obtain titanium silicalite molecular sieve catalyst with high performance, the method solves prior art to a certain extent and prepares that HTS cost is high, catalytic activity is low and the problem of poor stability, but is unfavorable for industrial applications due to preparation and modifying process complicated operation.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides the preparation of titanium-silicon molecular sieve catalyst and method of modifying and the application in ketoxime, not only can reduce cost prepared by HTS, effectively remove the extra-framework titanium in molecular sieve, significantly can improve the catalytic performance of cheap system molecular sieve in ketone oximation reaction simultaneously.
The technical solution used in the present invention is as follows:
The preparation of titanium-silicon molecular sieve catalyst and a method of modifying, the method comprises the following steps:
1) with titanium source, silicon source, the first template, the first alkali source, water and additive are raw material, add crystal seed, adopt hydrothermal synthesis method to prepare HTS A;
2) modified molecular screen B is obtained with the above-mentioned molecular sieve-4 A of acidic mixed solution modification;
3) with the second template and the second alkali source, or the mixed solution modified molecular screen B of the second template and ammonium salt obtains molecular sieve C.
Silicon source described in step 1) is silicon sol, and titanium source is tetrabutyl titanate, and the first template is 4-propyl bromide, and the first alkali source is n-Butyl Amine 99, and additive is hydrogen peroxide.
Prepare the raw material of HTS A as hydrothermal synthesis method after silicon source described in step 1) and titanium source adopt the hydrolysis of distribution hydrolysis method.
Step 2) described in acidic solution be the mixed aqueous solution of dilute hydrochloric acid or dilute sulphuric acid and hydrogen peroxide.
The second template described in step 3) is selected from TPAOH, 4-propyl bromide, and the second alkali source is selected from the aqueous solution of metal hydroxides, ammonia or organic amine, and ammonium salt is selected from ammonium sulfate, monoammonium sulfate, volatile salt or bicarbonate of ammonia.
Step 2) in the temperature of acidic solution modification be 60 DEG C, the treatment time is 4 ~ 6 hours.
The treatment temp of the mixed solution modification described in step 3) is 175 DEG C, and the treatment time is 12 hours.
In mixed solution described in step 3), the mol ratio of the second alkali source and the second template, ammonium salt and the second template is 0 ~ 1.33.
A purposes for the titanium-silicon molecular sieve catalyst that the preparation of described a kind of titanium-silicon molecular sieve catalyst and method of modifying obtain, is applied to ketoxime.
 
The beneficial effect that the present invention compared with prior art has:
1) owing to using, silicon sol is silicon source, 4-propyl bromide is template and catalyzer cost is decreased;
2) preparation of catalyzer and modification simple to operate, process easily controls;
3) can extra-framework titanium in effective elimination molecular sieve; Ammoximation reaction activity for ketone significantly improves.
Accompanying drawing explanation
Fig. 1 is catalyst A 1 isothermal adsorption, desorption curve;
Fig. 2 is catalyzer C2 isothermal adsorption, desorption curve;
Fig. 3 is the infrared spectrum of catalyst A 1 and C2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
HTS A synthesizes citing
Comparative example 1
At 35 DEG C, 18.00g silicon sol (25% ~ 30%) dropwise adds in the mixture of 4.40g TPABr and 24g distilled water under stirring, and stir hydrolysis 0.5h, the solution obtained is as solution 1; At 35 DEG C, 0.74gTBOT dropwise adds 5.90g Virahol, 1.20gH under stirring 2o 2(30%), in 4.50g n-Butyl Amine 99 and 9.0g water mixed liquid, stir hydrolysis 0.5h, the solution obtained is as solution 2, under vigorous stirring, solution 2 is added drop-wise in solution 1 slowly, add 0.30g TS-1 as crystal seed, be warming up to 50 DEG C of hydrolysis 2h simultaneously, continue to be warming up to 85 DEG C of hydrolysis, except alcohol 3h; The colloidal sol obtained moves to 175 DEG C of crystallization 72h in Hydrothermal Synthesis still, last suction filtration, washing, 110 DEG C of dryings, and 550 DEG C of roasting 6h obtain molecular sieve-4 A 1.Its isothermal adsorption, desorption curve and infrared spectrum are respectively as shown in Figure 1, Figure 3.
Comparative example 2
At 35 DEG C, 18.00g silicon sol (25% ~ 30%) dropwise adds in the mixture of 4.40g TPABr and 24g distilled water under stirring, and stir hydrolysis 0.5h, the solution obtained is as solution 1; At 35 DEG C, 0.74gTBOT dropwise adds 5.90g Virahol, 1.20gH under stirring 2o 2(30%), in 4.50g n-Butyl Amine 99 and 9.0g water mixed liquid, stir hydrolysis 0.5h, the solution obtained is as solution 2, under vigorous stirring, solution 2 is added drop-wise in solution 1 slowly, adds the 0.0645g aluminum isopropylate being dissolved in 3.0g Virahol, then adds 0.30g TS-1 as crystal seed, be warming up to 50 DEG C of hydrolysis 2h simultaneously, continue to be warming up to 85 DEG C of hydrolysis, except alcohol 3h; The colloidal sol obtained moves to 175 DEG C of crystallization 72h in Hydrothermal Synthesis still, last suction filtration, washing, 110 DEG C of dryings, and 550 DEG C of roasting 6h obtain molecular sieve-4 A 2.
Embodiment 1
Take 1.0g molecular sieve-4 A 1 and join 20mL 1M HCl solution and 2.5mL H 2o 2in, stir process 4h at 60 DEG C, after being cooled to room temperature, wash at 110 DEG C of dry 3h to neutrality, 550 DEG C of roasting 3h, obtain modifying titanium-silicon molecular sieve B1.
Embodiment 2 ~ 4
Preparation process with embodiment 1, concrete proportioning raw materials and acid reaction variables as shown in table 1, the sample number into spectrum obtaining modifying titanium-silicon molecular sieve catalyzer is B2 ~ B4.
Embodiment 5
Take 1.0g molecular sieve B1,1.0g TPAOH, 0.0149g NH 4hSO 4, and 20g water add in crystallizing kettle, after being uniformly mixed, 175 DEG C of crystallization 12h, after being cooled to room temperature, washing, dry, 550 DEG C of roasting 4h, obtain modifying titanium-silicon molecular sieve C1.
Embodiment 6 ~ 14
Preparation process with embodiment 5, concrete proportioning raw materials and modified condition as shown in table 2, the sample number into spectrum obtaining modifying titanium-silicon molecular sieve catalyzer is C2 ~ C10.The isothermal adsorption of catalyzer C2, desorption curve and infrared spectrum are respectively as shown in Figure 2 and Figure 3.
Embodiment 15
Carry out acid treatment to HTS A2, preparation process is with embodiment 1, and the catalyst sample obtained is numbered B5.
Embodiment 16
Carry out alkaline purification to HTS B5, preparation process is with embodiment 5, and the catalyst sample obtained is numbered C11.
Embodiment 17
Catalyzer after above-mentioned HTS and modification is used for cyclohexanone oxamidinating reaction evaluating, and detailed process is: temperature of reaction 75 DEG C, n (pimelinketone): n (H 2o 2): n (NH 3): n (TBA)=1.0:2.0:3.0:4.0, reaction times 5h, ammoniacal liquor is disposable to add, 8%H 2o 23.5h is dripped by syringe pump.The selectivity of pimelinketone transformation efficiency and cyclohexanone-oxime is in table 3.
Table 1 acid treatment and process rear catalyst numbering
Embodiment Acid kind Time/h Catalyzer is numbered
1 Hydrochloric acid 4 B1
2 Hydrochloric acid 6 B2
3 Sulfuric acid 4 B3
4 Sulfuric acid 6 B4
16 Hydrochloric acid 4 B5
Table 2 alkaline purification and process rear catalyst numbering
Embodiment Template Alkali/ammonium salt TS-1 (g): template: alkali/ammonium salt: water (g) Catalyzer is numbered
5 TPAOH Monoammonium sulfate 50:0.05:0.01:1000 C1
6 TPAOH Bicarbonate of ammonia 50:0.05:0.01:1000 C2
7 TPAOH Volatile salt 50:0.05:0.005:1000 C3
8 TPAOH Ammonium sulfate 50:0.05:0.005:1000 C4
9 TPAOH Nothing 50:0.05:1000 C5
10 TPABr Ammoniacal liquor 50:0.05:0.10:1000 C6
11 TPABr Sodium hydroxide 50:0.05:0.02:1000 C7
12 TPABr N-Butyl Amine 99 50:0.05:0.15:1000 C8
13 TPABr Quadrol 50:0.05:0.15:1000 C9
14 TPABr -- 50:0.05:1000 C10
15 TPAOH Monoammonium sulfate 50:0.05:0.01:1000 C11
Table 3 HTS is used for cyclohexanone oxamidinating reaction result
Sample number into spectrum Transformation efficiency (%) Selectivity (%) Yield (%)
A1 87.15 71.93 62.68
A2 93.59 84.61 79.18
B1 88.35 85.57 75.60
B2 89.23 85.64 76.41
B3 87.12 85.33 74.34
B4 87.45 85.92 75.14
B5 94.21 86.33 81.33
C1 99.90 87.90 87.81
C2 99.81 88.83 88.71
C3 99.15 87.18 86.44
C4 63.72 68.01 43.33
C5 98.23 83.34 81.86
C6 98.49 82.49 81.24
C7 99.23 88.94 88.26
C8 98.49 82.49 81.24
C9 98.32 82.11 80.73
C10 99.23 88.94 88.26
C11 99.75 90.11 89.88
A1 a 99.98 93.71 93.69
Reaction conditions: 1.0g pimelinketone, 0.2g catalyzer, 8.7g 8wt%H 2o 2, the 3.0g trimethyl carbinol, 2.8g ammoniacal liquor, 75 DEG C, 5h.
Reaction conditions a: 1.0g pimelinketone, 0.4g catalyzer, 8.7g 8wt%H 2o 2, the 3.0g trimethyl carbinol, 2.8g ammoniacal liquor, 75 DEG C, 5h.
Comparison sheet 3 data find, the HTS through sour modification is used for oximes selectivity obviously to be increased, and is increased to 85.57% by original 71.93%; After alkali modification, transformation efficiency and selectivity are increased to more than 99% and 89% respectively.When unmodified catalyst levels doubles, catalytic effect significantly increases, and transformation efficiency and selectivity are increased to more than 99.9% and 93.7% respectively.

Claims (9)

1. the preparation of titanium-silicon molecular sieve catalyst and a method of modifying, is characterized in that: the method comprises the following steps:
1) with titanium source, silicon source, the first template, the first alkali source, water and additive are raw material, add crystal seed, adopt hydrothermal synthesis method to prepare HTS A;
2) modified molecular screen B is obtained with the above-mentioned molecular sieve-4 A of acidic mixed solution modification;
3) with the second template and the second alkali source, or the mixed solution modified molecular screen B of the second template and ammonium salt obtains molecular sieve C.
2. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, it is characterized in that: the silicon source described in step 1) is silicon sol, titanium source is tetrabutyl titanate, and the first template is 4-propyl bromide, first alkali source is n-Butyl Amine 99, and additive is hydrogen peroxide.
3. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: the raw material preparing HTS A after the silicon source described in step 1) and titanium source adopt the hydrolysis of distribution hydrolysis method as hydrothermal synthesis method.
4. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: step 2) described in acidic solution be the mixed aqueous solution of dilute hydrochloric acid or dilute sulphuric acid and hydrogen peroxide.
5. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, it is characterized in that: the second template described in step 3) is selected from TPAOH, 4-propyl bromide, second alkali source is selected from the aqueous solution of metal hydroxides, ammonia or organic amine, and ammonium salt is selected from ammonium sulfate, monoammonium sulfate, volatile salt or bicarbonate of ammonia.
6. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: step 2) in the temperature of acidic solution modification be 60 DEG C, the treatment time is 4 ~ 6 hours.
7. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: the treatment temp of the mixed solution modification described in step 3) is 175 DEG C, and the treatment time is 12 hours.
8. the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: in the mixed solution described in step 3), the mol ratio of the second alkali source and the second template, ammonium salt and the second template is 0 ~ 1.33.
9. the purposes of titanium-silicon molecular sieve catalyst that obtains of the preparation of a kind of titanium-silicon molecular sieve catalyst according to claim 1 and method of modifying, is characterized in that: be applied to ketoxime.
CN201410514259.8A 2014-09-30 2014-09-30 Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation Pending CN104291352A (en)

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CN104815689A (en) * 2015-03-17 2015-08-05 河南弘康清洁能源股份有限公司 HPPO catalyst production process
CN105921171A (en) * 2016-04-29 2016-09-07 山西大学 Method for improving stability of cyclohexanone ammoximation catalyst TS-1 molecular sieves
CN106348310A (en) * 2016-08-17 2017-01-25 巨化集团技术中心 Preparation method and application of titanium-silicalite-molecular-sieve polymer
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CN114426500A (en) * 2020-09-21 2022-05-03 中国石油化工股份有限公司 Method for preparing ketoxime by ketoammoximation
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Application publication date: 20150121