CN115007202A - Preparation method and application of cyclohexanone ammoxidation catalyst - Google Patents

Preparation method and application of cyclohexanone ammoxidation catalyst Download PDF

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CN115007202A
CN115007202A CN202210754521.0A CN202210754521A CN115007202A CN 115007202 A CN115007202 A CN 115007202A CN 202210754521 A CN202210754521 A CN 202210754521A CN 115007202 A CN115007202 A CN 115007202A
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cyclohexanone
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马楠
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Gerun Technology Dalian Co ltd
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    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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    • 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
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Abstract

The invention discloses a preparation method and application of cyclohexanone ammoxidation catalyst, wherein the cyclohexanone ammoxidation catalyst is a titanium silicalite TS-1, and the titanium silicalite TS-1 is synthesized by adopting tetrabutoxy titanium tetramer as a titanium source in a low-cost template system. The catalyst prepared by the method is a micron-sized molecular sieve with uniform granularity and regular shape, and isolated four-coordinated titanium (Ti) species on the molecular sieve are relatively more, so that the catalyst shows excellent catalytic activity in the process of catalyzing cyclohexanone ammoxidation.

Description

Preparation method and application of cyclohexanone ammoxidation catalyst
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a preparation method and application of a cyclohexanone ammoxidation catalyst.
Background
Cyclohexanone oxime is an intermediate product in the production process of caprolactam, the synthesized caprolactam product is an important chemical raw material, most of caprolactam is used for producing polycaprolactam, about 90 percent of the polycaprolactam is used for producing synthetic fibers, namely carpron, and 10 percent of the polycaprolactam is used as plastic and is used for manufacturing gears, bearings, pipes, medical instruments, electrical and insulating materials and the like. Also used for coating, plastic agent and little used for synthesizing lysine, etc. It can also be used to prepare caprolactam resin, fiber and artificial leather, etc., and also can be used as medicine raw material.
The most interesting production process of cyclohexanone oxime is the technology developed by Montedipe company in Italy in the 80 th century, namely cyclohexanone, ammonia and hydrogen peroxide are subjected to ammoximation reaction under the action of a TS-1 molecular sieve catalytic material to directly prepare the cyclohexanone oxime in one step with high selectivity. The process is simple, mild in condition, less in three wastes and environment-friendly.
The TS-1 molecular sieve has excellent catalytic performance in the aspect of low-temperature selective oxidation, and is one of the research hotspots of green chemistry for many years. It is generally believed that isolated tetracoordinated titanium (Ti) species on the TS-1 molecular sieve are the active sites for catalytic oxidation reactions. The preparation method of the TS-1 molecular sieve can be divided into a classical method and a cheap method. The TS-1 molecular sieve synthesized by the classical method has more isolated four-coordinate titanium (Ti) species and good catalytic performance. However, the use of expensive template and silicon source results in high production cost of the molecular sieve of the classical method, which limits its industrial application. The cheap method is as the name implies, the template agent and the silicon source which are cheap are adopted in the synthesis process, and the synthesis cost of the TS-1 molecular sieve is low. However, the coordination situation of Ti in the TS-1 molecular sieve prepared by the cheap method is not ideal as that of the classical method, and isolated four-coordination titanium (Ti) species are few, so the catalytic activity is low. In the synthesis process of the TS-1 molecular sieve, the mismatching of the hydrolysis rates of a silicon source and a titanium source is an important factor influencing the catalytic performance of the molecular sieve. Generally, the silicon source has a slow hydrolysis rate and the titanium source has a fast hydrolysis rate. The faster hydrolysis rate of the titanium source leads part of the titanium to generate non-skeleton Titanium (TiO) because of the too fast hydrolysis 2 ) Or anatase, and thus deteriorates the catalytic performance of the TS-1 molecular sieve.
TS-1 is taken as a heteroatom molecular sieve with MFI structure, and isolated four-coordination framework titanium is the most widely accepted catalytic active center by researchers at present. A number of patents and articles disclose methods for preparing TS-1 zeolites enriched in isolated framework titanium species, such as: patent CN109250726B discloses that a preparation has highThe method of the titanium silicalite TS-1 with the framework titanium content comprises the following specific steps: mixing a silicon source and a titanium source in proportion, and adding a quaternary ammonium alkali aqueous solution to obtain a mixed solution; hydrolyzing the mixed solution to remove alcohol, adding a starch solution, and crystallizing to obtain a crystallized product; and drying and roasting the crystallized product to obtain the titanium silicalite TS-1 with high framework titanium content. According to the method, a starch solution is added in the synthesis process, and a silicon source and a titanium source are bridged by using a large amount of hydroxyl contained in the starch, so that the silicon source and the titanium source are more easily combined, and more titanium can enter a TS-1 framework. The titanium silicalite molecular sieve prepared by the method has high framework titanium content, almost does not contain non-framework titanium, and the mother liquor can be recycled. Patent CN104528761B discloses a method for synthesizing a titanium silicalite molecular sieve with high framework titanium content, which comprises the steps of dealcoholizing step by step, adding a proper amount of aliphatic amine compounds into the molecular sieve after pre-crystallization, and then continuing hydrothermal crystallization, so as to reduce the loss of framework titanium in the synthesis process of the molecular sieve and avoid the formation of non-framework titanium. The article JAm Chem Soc,2008,130: 10150-10164 discloses a synthesis method of TS-1 zeolite, and researches the influence of different ammonium carbonate addition amounts on the crystallization process of the TS-1 zeolite. Research shows that the content of isolated four-coordination framework titanium species in the TS-1 zeolite can be effectively improved by adding a proper amount of ammonium carbonate. An article J Mater Chem A,2018,6: 9473-9479 discloses a synthesis method of TS-1 zeolite, wherein Triton X-100 is added into a molecular sieve precursor solution to reduce the crystallization rate of a molecular sieve (namely, the generation rate of an MFI molecular sieve structure is reduced), and meanwhile, rotational crystallization is introduced to improve the dispersion condition of titanium species in sol, so that non-framework Titanium (TiO) is inhibited 2 ) The generation of the titanium complex effectively improves the content of the titanium species with the four-coordination framework.
As can be seen from the above research, the existing method for preparing TS-1 zeolite rich in isolated four-coordination framework titanium species is mainly realized by adding additives such as starch, fatty amines, ammonium carbonate, Triton X-100 and the like to match the hydrolysis rates of silicon and a titanium source.
Disclosure of Invention
In order to make up for the non-framework Titanium (TiO) in the TS-1 molecular sieve prepared by the prior cheap method 2 ) In a large amount, four pairs in isolationThe invention provides a method for synthesizing a TS-1 molecular sieve, which has the defects of insufficient site-skeleton titanium species and the need of additionally adding an additive to improve the content of a four-coordinate skeleton titanium species. The TS-1 molecular sieve prepared by the method has high framework titanium content and shows excellent catalytic activity in the process of catalyzing cyclohexanone ammoxidation.
The invention is realized by the following technical scheme:
a preparation method of cyclohexanone ammoxidation catalyst comprises the following steps:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a solution A;
(2) uniformly mixing the tetrabutoxytitanium tetramer with a complexing agent, dropwise adding the mixture into the solution A, and uniformly stirring to obtain a solution B;
(3) adding a mineralizer into the solution B, and supplementing water to obtain a solution C;
(4) the solution C is put into a crystallization kettle and crystallized for 20 to 120 hours at the temperature of 150 ℃ and 210 ℃; and filtering, separating, drying and roasting the obtained crystallized product to obtain the cyclohexanone ammoxidation catalyst (titanium silicalite TS-1).
Preferably, the dropping time in the step (1) is 1-6 h.
As a preferred scheme, the silicon source is one or more of silica sol, white carbon black and silica gel, and further preferably silica sol.
Preferably, the template agent is one or more of tetrapropylammonium bromide (TPABr), tetrapropylammonium chloride (TPACl) and tetrapropylammonium fluoride (TPAF), and more preferably tetrapropylammonium bromide.
Preferably, the complexing agent is one of isopropanol, acetylacetone and ethanol.
Preferably, the mineralizer is one or more of ammonia water, methylamine, ethylamine, n-propylamine, ethylenediamine, diethylamine, hexamethylenediamine and n-butylamine.
Preferably, the molar ratio of each substance in the solution C is: SiO 2 2 ：TiO 2 ：TPA + : mineralizing agent: h 2 O＝1:(0.02-0.033):(0.25-0.4):(1.8-3.5):(20-25)。
The invention also provides the application of the catalyst obtained by the method in cyclohexanone ammoxidation, wherein the contact time of the catalyst with the concentration of 1-10% (mass percent, accounting for the total mass of reactants) in a reactor is 60-100min under the conditions that the temperature of reaction materials is 60-90 ℃ and the normal pressure is 0.6 Mpa; the molar ratio of the hydrogen peroxide to the cyclohexanone in the reaction materials is 0.8-1.3: 1; the mol ratio of ammonia to cyclohexanone is 1.1-2.6: 1; the molar ratio of the solvent to the cyclohexanone is 1.0-5.0.
Preferably, the pressure is 0.2-0.45 MPa; the concentration of the catalyst is 2-5%, the molar ratio of the hydrogen peroxide to the cyclohexanone is 1.0-1.15:1, and the molar ratio of the ammonia to the cyclohexanone is 1.4-2.2: 1; the molar ratio of the solvent to the cyclohexanone is 2.0-4.0.
The method has the beneficial effects that the tetrabutoxy titanium tetramer (also called tetrabutyl titanate tetramer) is used as the titanium source, and because the tetrabutoxy titanium tetramer is a titanium source in a polymerization state, the hydrolysis rate is slower than that of the tetrabutyl titanate of a monomer during hydrolysis and is matched with the silicon source with slow hydrolysis, so that Ti of the silicon source and the titanium source with approximate hydrolysis rates can better enter a zeolite framework in the crystallization process under the action of a template agent, the production of non-framework titanium and anatase caused by over-fast hydrolysis of the titanium source is reduced, and the TS-1 molecular sieve with excellent performance is obtained. The method has the following characteristics:
1. green and environment-friendly, and does not need various additives (starch, fatty amines, ammonium carbonate and Triton X-100).
2. The synthesis method is simple and efficient. The operation difficulty is reduced, the synthesis operation process is simplified, and the industrial amplification of the synthesis of the titanium silicalite molecular sieve is facilitated. The traditional method for synthesizing the titanium silicalite molecular sieve needs to strictly control the dropping rate of a titanium source, needs longer time, and generally needs at least 6 hours to prepare glue solution required by synthesis. When the method is used for synthesizing the titanium silicalite molecular sieve, the requirement on the dropping speed of a titanium source is relaxed, and the dropping time is 1-6 h.
3. The catalyst has uniform particle size, regular shape and low separation energy consumption, reduces the preparation cost of the molecular sieve and is beneficial to industrial popularization.
4. The molecular sieve has more isolated four-coordinate Ti species, so the activity of the TS-1 molecular sieve is higher.
Drawings
FIG. 1 is an XRD pattern of a sample, where a is the XRD pattern of comparative example 1 and b is the XRD pattern of example 1.
FIG. 2 is a graph of the UV-Vis spectra of samples, wherein a is the UV-Vis spectrum of comparative example 1 and b is the UV-Vis spectrum of example 1;
fig. 3 is an SEM photograph of a sample, wherein a is an SEM photograph of comparative example 1, and b is an SEM photograph of example 1.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto. The reagents used in the examples are all commercially available chemical reagents.
Comparative example 1
Adding 200g of deionized water into 225g of silica sol (30% wt), stirring for 15min, adding 20.8g of tetrapropyl ammonium bromide into the glue solution, and continuously stirring for 30min to obtain a raw material silicon solution; mixing tetrabutyl titanate and acetylacetone in a mass ratio of 1:1, and stirring for 10min to obtain a raw material titanium solution; 15.4ml of the prepared titanium source is dripped into the raw material silicon solution for 6 hours, then the silicon-titanium solution is obtained after stirring for 30min, 52ml of n-butylamine is added, 145g of deionized water is supplemented, and stirring is continued for 60min to obtain a uniform silicon-titanium solution; then adding the obtained solution into a 2L stainless steel reaction kettle, and crystallizing for 60 hours under the autogenous pressure and the temperature of 170 ℃; and filtering the product by a conventional method, washing to be neutral, drying at 100 ℃, roasting at 540 ℃ for 6h, removing the template agent to obtain a molecular sieve sample TS-1-A, wherein XRD (X-ray diffraction) characterization is shown in figure 1(a), and the product has a typical MFI topological structure and good relative crystallinity.
The ultraviolet visible spectrum is shown in figure 2(a), except that the absorption peak of the four-coordination framework titanium exists at 190-210 nm, a wide absorption peak exists at 270-280 nm in the ultraviolet spectrum, and the existence of amorphous six-coordination non-framework titanium is indicated. The absorption band of anatase is clearly present at 330 nm.
As shown in FIG. 3(a), the scanning electron microscope showed a long plate-like molecular sieve having amorphous material on the surface and a size of about 30 μm.
Example 1
Comparative example 1 was repeated, but the titanium source was replaced by tetrabutyltitanate tetramer, the mass ratio of titanium source to complexing agent being 1: 1.5, the adding amount is 22.8ml, the titanium source is added for 3h, and a molecular sieve sample TS-1-B is obtained, as shown in figure 1(B), XRD (X-ray diffraction) is characterized by having a typical MFI topological structure and good relative crystallinity.
The ultraviolet visible spectrum is shown in figure 1(b), the ultraviolet spectrum has a sharp absorption peak of four-coordination framework titanium at 190-210 nm, and the absorption peak at 270-280 nm is not obvious, which shows that the content of amorphous six-coordination non-framework titanium is greatly reduced. The absorption band of anatase at 330nm is not evident.
The scanning electron micrograph is shown in FIG. 2(b), and is a thin plate-like molecular sieve with smooth surface, uniform particles, and a size of about 1.2. mu.m.
Example 2
Comparative example 1 was repeated, but the titanium source was replaced by tetrabutyltitanate tetramer, the mass ratio of titanium source to complexing agent being 1: 1.5, the adding amount is 22.8ml, the dropping time of the titanium source is 1h, and a molecular sieve sample TS-1-C is obtained. The XRD, uv and sem characterization results of the obtained samples were similar to those of example 1.
Example 3
Example 2 was repeated, but the silicon source was replaced by silica gel, fumed silica, and the amounts of the component materials were kept constant, to obtain molecular sieve products TS-1-D and TS-1-E in this order. The XRD, uv and sem characterization results of the obtained samples were similar to those of example 1.
Example 4
Example 2 was repeated, but the template was replaced with tetrapropylammonium chloride, tetrapropylammonium fluoride, keeping the amounts of the component substances unchanged, to obtain molecular sieve products TS-1-F and TS-1-G in this order. The XRD, uv and sem characterization results of the obtained samples were similar to those of example 1.
Example 5
Example 2 was repeated, but the complexing agent was replaced by isopropanol, ethanol, and the amounts of the component substances were kept constant, to obtain molecular sieve products TS-1-H and TS-1-I in this order. The XRD, uv and sem characterization results of the obtained samples were similar to those of example 1.
Example 6
Example 2 was repeated, but the n-butylamine was replaced with ammonia, methylamine, ethylamine, n-propylamine, ethylenediamine, diethylamine, hexamethylenediamine, respectively, while keeping the amounts of the component substances constant, to obtain molecular sieve products TS-1-J, TS-1-K, TS-1-L, TS-1-M, TS-1-N, TS-1-O and TS-1-P in this order. The XRD, uv and sem characterization results of the obtained samples were similar to those of example 1.
Example 7
The molecular sieve sample is subjected to catalytic performance evaluation under the following conditions:
the feeding speed of cyclohexanone is 130g/h, the feeding speed of solvent tert-butyl alcohol is 450g/h, the feeding speed of 30 wt% of hydrogen peroxide is 150g/h, the feeding speed of ammonia (99.99%) is 45g/h, the mass concentration of the titanium-silicon molecular sieve is 4.0%, the average retention time of materials in a reactor is 80min, the reaction temperature is 80 ℃, the reaction pressure is 0.3MPa, back flushing is performed in the filter every 25s, and the result after 60h of reaction is shown in Table 1.
TABLE 1 cyclohexanone ammoxidation performance results for the TS-1 samples of examples 1-6 and comparative example 1
Samples C Cyclohexanone ％ S Cyclohexanone oxime ％
TS-1-A 52.1 83.2
TS-1-B 65.3 92.3
TS-1-C 65.5 92.8
TS-1-D 65.1 92.5
TS-1-E 65.8 92.4
TS-1-F 65.6 92.5
TS-1-G 65.5 92.7
TS-1-H 65.5 92.3
TS-1-I 65.4 92.5
TS-1-J 65.3 92.4
TS-1-K 65.6 92.3
TS-1-L 655 92.4
TS-1-M 65.7 92.6
TS-1-N 65.5 92.7
TS-1-O 65.6 92.5
TS-1-P 65.5 92.6
As can be seen from the results in the table, the cyclohexanone ammoxidation performance of the TS-1 molecular sieve catalyst obtained by using tetrabutyl titanate as titanium ester is obviously lower than that of the catalyst obtained by using tetramer of tetrabutyl titanate as a titanium source under the same condition, and the polymeric substance is used as the titanium source, so that the hydrolysis rate of Ti is obviously reduced, the TS-1 molecular sieve with higher isolated Ti content is obtained, and the activity of the catalyst is greatly improved.

Claims (8)

1. A preparation method of cyclohexanone ammoxidation catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly mixing a silicon source, a template agent and deionized water to obtain a solution A;
(2) uniformly mixing the tetrabutoxytitanium tetramer with a complexing agent, dropwise adding the mixture into the solution A, and uniformly stirring to obtain a solution B;
(3) adding a mineralizer into the solution B, and supplementing water to obtain a solution C;
(4) the solution C is put into a crystallization kettle and crystallized for 20 to 120 hours at the temperature of 150-; and filtering, separating, drying and roasting the crystallized product to obtain the cyclohexanone ammoxidation catalyst.
2. The process according to claim 1, wherein the cyclohexanone ammoxidizing catalyst is prepared by: the dripping time in the step (2) is 1-6 h.
3. The process for preparing a cyclohexanone ammoxidation catalyst according to claim 1, wherein: the silicon source is one or more of silica sol, white carbon black and silica gel.
4. The process according to claim 1, wherein the cyclohexanone ammoxidizing catalyst is prepared by: the template agent is one or more of tetrapropylammonium bromide, tetrapropylammonium chloride and tetrapropylammonium fluoride.
5. The process for preparing a cyclohexanone ammoxidation catalyst according to claim 1, wherein: the complexing agent is one of isopropanol, acetylacetone and ethanol.
6. The process according to claim 1, wherein the cyclohexanone ammoxidizing catalyst is prepared by: the mineralizer is one or more of ammonia water, methylamine, ethylamine, n-propylamine, ethylenediamine, diethylamine, hexamethylenediamine and n-butylamine.
7. The process for producing a cyclohexanone ammoxidizing catalyst according to claim 1 or 4, wherein: the molar ratio of the substances in the solution C is as follows: SiO 2 2 ：TiO 2 ：TPA + : a mineralizer: h 2 O＝1:(0.02-0.033):(0.25-0.4):(1.8-3.5):(20-25)。
8. Use of the catalyst obtained by the process according to claim 1 for the ammoxidation of cyclohexanone, characterized in that: contacting the reaction materials in a reactor for 60-100min under the conditions of 60-90 ℃ and normal pressure to 0.6Mpa, wherein the catalyst with the mass concentration of 1-10 percent is in contact with the reaction materials in the reactor; the molar ratio of the hydrogen peroxide to the cyclohexanone in the reaction materials is (0.8-1.3): 1, the molar ratio of ammonia to cyclohexanone is (1.1-2.6) to 1; the molar ratio of the solvent to the cyclohexanone is 1.0-5.0.
CN202210754521.0A 2022-06-30 2022-06-30 Preparation method and application of cyclohexanone ammoxidation catalyst Pending CN115007202A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
CN108793181A (en) * 2017-12-15 2018-11-13 中国科学院大连化学物理研究所 A kind of Titanium Sieve Molecular Sieve and preparation and application
CN112871206A (en) * 2021-01-19 2021-06-01 中国科学院大连化学物理研究所 Preparation method of low-cost high-activity phenol hydroxylation titanium silicalite molecular sieve catalyst

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN108793181A (en) * 2017-12-15 2018-11-13 中国科学院大连化学物理研究所 A kind of Titanium Sieve Molecular Sieve and preparation and application
CN112871206A (en) * 2021-01-19 2021-06-01 中国科学院大连化学物理研究所 Preparation method of low-cost high-activity phenol hydroxylation titanium silicalite molecular sieve catalyst

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Title
RISHENG BAI等: "Titanium-rich TS-1 zeolite for highly efficient oxidative desulfurization", GREEN ENERGY & ENVIRONMENT, vol. 8, 11 March 2021 (2021-03-11), pages 163 - 172 *
邵秀丽;: "TS-1分子筛催化剂的制备和表征", 工业催化, no. 12, 15 December 2016 (2016-12-15), pages 36 - 40 *

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