A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve

Abstract

The present invention relates to the field of chemical industry, and specifically to a preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve; the method provides a method for preparing butanone oxime by ammoxidation reaction of butanone, and the method uses butanone as a raw material, catalyzes ammoxidation to generate butanone oxime, and has the advantages of being clean and pollution-free. The method uses a nickel-doped titanium silicon molecular sieve catalyst as a catalyst for catalytic ammoxidation of butanone, which can not only improve the conversion rate and selectivity of butanone, but also is a green chemical process, and the only by-product of the process is water, eliminating the defects of the traditional method such as many by-products and complicated operation steps.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a preparation method for producing butanone oxime by using nickel-doped titanium silicon molecular sieve. Background Art

[0002] As an important chemical raw material, butanone oxime is often used in anti-skinning agents for inks, paints, and coatings due to its low pollution and low toxicity. It can also be used as a chemical deoxidizer for boiler water and an intermediate for building materials. Traditionally, the hydroxylamine method is used for production, that is, hydroxylamine salts react with ketones to produce oximes, and then ammonia water is used for neutralization and separation to obtain the product. This method is complex, greatly affected by external environmental factors, and requires high energy consumption, and has gradually become unsuitable for chemical production.

[0003] Since 1983, a patent reported that nickel-doped titanium silicalite was used as a catalyst and dilute hydrogen peroxide (H2O2 mass fraction is 30%) as an oxidant to catalyze the oxidation of phenol and produce o- and hydroquinone at the same time, there have been many reports on the hydroxylation reaction of molecular sieve catalysts, and the research has been the most thorough. The birth of nickel-doped titanium silicalite has set off a revolution in the heterogeneous selective catalytic oxidation of organic matter, especially for the selective oxidation under mild conditions with dilute hydrogen peroxide solution as an oxidant. It has unique performance. Nickel-doped titanium silicalite catalyst makes the reaction have the following significant advantages: ① Mild reaction conditions, can be carried out at normal pressure and low temperature of 20-100℃; ② High yield of oxidation target product and good selectivity; ③ Simple process; ④ Since low-concentration hydrogen peroxide is used as an oxidant, the oxidation source is safe and easy to obtain; ⑤ The reduction product is H202, and the reaction system does not introduce impurities and will not cause environmental pollution. Its successful development is considered a milestone in zeolite catalysis in the 1980s, laying the foundation for the study of highly selective hydrocarbon oxidation reactions and the development of green processes.

[0004] The synthesis methods of nickel-doped titanium silicon molecular sieve are generally divided into two categories: direct hydrothermal synthesis and secondary synthesis isomorphous substitution. Hydrothermal synthesis is a classic synthesis method, but the raw materials are expensive, the method is complicated, and the cycle is long; while the goal of indirect synthesis technology is to obtain high-quality nickel-doped titanium silicon molecular sieves with cheap raw materials and simple methods. Summary of the invention

[0005] The purpose of the present invention is to provide a preparation method for butanone oxime using nickel-doped titanium silicon molecular sieve, wherein butanone is used as a raw material, a nickel-doped titanium silicon molecular sieve catalyst is selected as a catalyst for catalytic ammoxidation of butanone, and butanone oxime is generated by catalytic ammoxidation. The method has the advantages of being clean and pollution-free, and can improve the conversion rate and selectivity of butanone.

[0006] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0007] A nickel-doped titanium silicon molecular sieve catalyst and butanone are stirred and mixed evenly, and then the feed liquid is added to a reactor, and then ammonia water (25%) and hydrogen peroxide (35%) are added; the reaction temperature is 60-80°C, and the reaction time is 0.5-5h to generate a reaction liquid mixture; the mixture is sent to a separator for stratification into organic and inorganic phases, and the upper organic phase is the product butanone oxime; the characteristic is that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0008] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0009] S1: According to the mass fraction, 30-40 parts of high silicon or full silicon zeolite molecular sieve are first dealuminated with 10%-20% dilute hydrochloric acid at a temperature of 700-900°C in a quartz tube fixed bed reactor to produce vacancies in the framework, and then 50-60 parts of TiCl4 are brought into the reactor with N2, and the isomorphous substitution reaction time is 1-5h at a temperature of 400-700°C, and titanium is inserted. After cooling and drying, a nickel-doped titanium silicon molecular sieve catalyst is obtained.

[0010] S2: 15-25 parts of nickel-doped titanium silicon molecular sieve catalyst, 3-7 parts of aminosilane, 100-120 parts of DMF, stirred at 50-70°C for 120-160 minutes,

[0011] S3: adding 1.5-3.5 parts of nickel acrylate, 0.02-0.8 parts of 4-propylenethiosemicarbazide, and 0.1-2.1 parts of an organic base, stirring at 60-70° C. for 120-160 minutes, filtering, and drying to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0012] Preferably, the concentration of the catalyst in the reaction solution is 0.5-5wt%.

[0013] The molar ratio of the ketone to the hydrogen peroxide is 1:1.05-1.3; the molar ratio of the ketone to ammonia is 1:1.05-1.25.

[0014] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0015] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0016] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0017] The aminosilane coupling agent is KH550, KH540, KH551, KH902, KH791 or KH792.

[0018] The organic base is, for example, ethanolamine, diethanolamine, triethanolamine.

[0019] Reaction mechanism:

[0020] The reaction formula for preparing butanone oxime by ammoxidation of butanone is as follows:

[0021]

[0022] Using high silicon or full silicon zeolite molecular sieve as silicon source and TiCl4 as titanium source, the reaction formula for preparing nickel-doped titanium silicon molecular sieve catalyst by gas-solid isomorphous substitution is as follows:

[0023]

[0024] Technical effect:

[0025] The invention discloses a method for preparing a nickel-doped titanium silicon molecular sieve for producing butanone oxime. The method provides a method for preparing butanone oxime by ammoxidation reaction of butanone. The method uses butanone as a raw material and catalyzes ammoxidation to generate butanone oxime, which has the advantages of being clean and pollution-free. The method uses a nickel-doped titanium silicon molecular sieve catalyst as a catalyst for catalytic ammoxidation of butanone, which can not only improve the conversion rate and selectivity of butanone, but also is a green chemical process, and the only byproduct of the process is water, eliminating the defects of the traditional method such as many byproducts and complicated operation steps.

[0026] At the same time, the method also provides a method for preparing nickel-doped titanium silicon molecular sieve by gas-solid isomorphous substitution. This method will definitely replace the traditional hydrothermal synthesis method due to its advantages of simple preparation, cheap raw materials and stable performance. The main performances are:

[0027] (1) Various reagents are easy to obtain and the preparation is reproducible:

[0028] (2) The introduction of titanium is relatively easy to achieve and has a certain adjustment range. The generation of non-framework titanium is relatively easy to control and can reach the level of the direct method.

[0029] (3) The prospects for industrial applications are optimistic;

[0030] (4) It can be easily extended to other types of molecular sieves, such as Ti3. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The butanone oxime chromatogram prepared in Example 1;

[0032] Figure 2 This is the chromatogram of butanone oxime prepared in Example 4. DETAILED DESCRIPTION

[0033] The invention will be further described below by means of specific embodiments:

[0034] The composition of the product was analyzed by high performance gas chromatography.

[0035] The sample was vaporized and passed through a chromatographic column to separate butanone oxime from other components. The sample was monitored by a flame ionization detector and the mass fraction of butanone oxime was calculated by the area normalization method.

[0036] The purity (x) of butanone oxime, expressed as mass fraction (%), is calculated according to the following formula (the result is rounded to two decimal places).

[0037] X=(A / ΣAi)×100%

[0038] Where: A is the value of the peak area of ​​butanone oxime in the sample, uV·S; A is the value of the peak area of ​​each component in the sample, uV·S.

[0039] Example 1

[0040] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0041] 4g of nickel-doped titanium silicon molecular sieve catalyst and 50g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 50g of ammonia water and 78g of hydrogen peroxide were added. The reaction temperature was 60°C and the reaction time was 1h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; the characteristic is that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0042] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0043] S1: In a quartz tube fixed bed reactor, 30g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 10% dilute hydrochloric acid at 700°C to create vacancies in the framework, and then 50g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 400°C for 1h, and titanium is inserted. After cooling and drying, a nickel-doped titanium silicon molecular sieve catalyst is obtained.

[0044] S2: 15g nickel-doped titanium silicon molecular sieve catalyst, 3g aminosilane, 100g DMF, stirred at 50°C for 120 minutes,

[0045] S3: Add 1.5 g of nickel acrylate, 0.02 g of 4-propylenethiosemicarbazide, and 0.1 g of an organic base, stir at 60° C. for 120 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0046] The mass fraction of the ammonia water is 25%.

[0047] The mass fraction of the hydrogen peroxide is 35%.

[0048] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0049] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0050] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0051] The aminosilane coupling agent is KH550.

[0052] The organic base is ethanolamine.

[0053] The conversion rate of butanone in this experiment was 91.97%, and the selectivity of butanone oxime was 99.64%.

[0054] Example 2

[0055] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0056] 6g of nickel-doped titanium silicon molecular sieve catalyst and 55g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 57g of ammonia water and 82g of hydrogen peroxide were added. The reaction temperature was 65°C and the reaction time was 2h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; the characteristic is that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0057] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0058] S1: In a quartz tube fixed bed reactor, 33g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 13% dilute hydrochloric acid at 780°C to create vacancies in the framework, and then 53g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 500°C for 2h, followed by titanium insertion, cooling and drying to obtain a nickel-doped titanium silicon molecular sieve catalyst.

[0059] S2: 18g nickel-doped titanium silicon molecular sieve catalyst, 4g aminosilane, 106g DMF, stirred at 58°C for 130 minutes,

[0060] S3: Add 2 g of nickel acrylate, 0.3 g of 4-propylenethiosemicarbazide, and 0.8 g of an organic base, stir at 63° C. for 130 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0061] The mass fraction of the ammonia water is 25%.

[0062] The mass fraction of the hydrogen peroxide is 35%.

[0063] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0064] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0065] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0066] The aminosilane coupling agent is KH540.

[0067] The organic base is diethanolamine.

[0068] The conversion rate of butanone in this experiment was 97.31%, and the selectivity of butanone oxime was 99.85%.

[0069] Example 3

[0070] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0071] 10g of nickel-doped titanium silicon molecular sieve catalyst and 64g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 70g of ammonia water and 103g of hydrogen peroxide were added. The reaction temperature was 70°C and the reaction time was 3h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; it is characterized in that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0072] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0073] S1: In a quartz tube fixed bed reactor, 36g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 16% dilute hydrochloric acid at 830°C to create vacancies in the framework, and then 56g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 600°C for 3h, followed by titanium insertion, cooling and drying to obtain a nickel-doped titanium silicon molecular sieve catalyst.

[0074] S2: 22g nickel-doped titanium silicon molecular sieve catalyst, 5g aminosilane, 116g DMF, stirred at 68°C for 140 minutes,

[0075] S3: Add 3 g of nickel acrylate, 0.6 g of 4-propylenethiosemicarbazide, and 1.8 g of an organic base, stir at 66° C. for 150 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0076] The mass fraction of the ammonia water is 25%.

[0077] The mass fraction of the hydrogen peroxide is 35%.

[0078] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0079] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0080] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0081] The aminosilane coupling agent is KH551.

[0082] The organic base is, for example, triethanolamine.

[0083] The conversion rate of butanone in this experiment was 99.27%, and the selectivity of butanone oxime was 99.96%.

[0084] Example 4

[0085] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0086] 15g of nickel-doped titanium silicon molecular sieve catalyst and 80g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 94g of ammonia water and 140g of hydrogen peroxide were added. The reaction temperature was 80°C and the reaction time was 5h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; it is characterized in that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0087] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0088] S1: In a quartz tube fixed bed reactor, 40g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 20% dilute hydrochloric acid at 900°C to create vacancies in the framework, and then 60g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 700°C for 5h, followed by titanium insertion, cooling and drying to obtain a nickel-doped titanium silicon molecular sieve catalyst.

[0089] S2: 25g nickel-doped titanium silicon molecular sieve catalyst, 7g aminosilane, 120g DMF, stirred at 70°C for 160 minutes,

[0090] S3: Add 3.5 g of nickel acrylate, 0.8 g of 4-propylenethiosemicarbazide, and 2.1 g of an organic base, stir at 70° C. for 160 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0091] The mass fraction of the ammonia water is 25%.

[0092] The mass fraction of the hydrogen peroxide is 35%.

[0093] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0094] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0095] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0096] The aminosilane coupling agent is KH902.

[0097] The organic base is triethanolamine.

[0098] The conversion rate of butanone in this experiment was 99.86%, and the selectivity of butanone oxime was 99.98%.

[0099] Comparative Example 1

[0100] A preparation method for producing butanone oxime, the operating steps are:

[0101] 80g of butanone was stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 94g of ammonia water and 140g of hydrogen peroxide were added. The reaction temperature was 80°C and the reaction time was 5h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime.

[0102] The mass fraction of the ammonia water is 25%.

[0103] The mass fraction of the hydrogen peroxide is 35%.

[0104] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0105] In this experiment, the conversion rate of butanone was 3.02%, and the selectivity of butanone oxime was 0%.

[0106] Comparative Example 2

[0107] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0108] 15g of nickel-doped titanium silicon molecular sieve catalyst and 80g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 94g of ammonia water and 140g of hydrogen peroxide were added. The reaction temperature was 80°C and the reaction time was 5h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; it is characterized in that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0109] The nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0110] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0111] S1: In a quartz tube fixed bed reactor, 30g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 10% dilute hydrochloric acid at 700°C to create vacancies in the framework, and then 50g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 400°C for 1h, and titanium is inserted. After cooling and drying, a nickel-doped titanium silicon molecular sieve catalyst is obtained.

[0112] S2: 15g nickel-doped titanium silicon molecular sieve catalyst, 3g aminosilane, 100g DMF, stirred at 50°C for 120 minutes,

[0113] S3: Add 1.5 g of nickel acrylate, 0.02 g of 4-propylenethiosemicarbazide, and 0.1 g of an organic base, stir at 60° C. for 120 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0114] The mass fraction of the ammonia water is 25%.

[0115] The mass fraction of the hydrogen peroxide is 35%.

[0116] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0117] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0118] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0119] The aminosilane coupling agent is KH550.

[0120] The organic base is ethanolamine.

[0121] In this experiment, the conversion rate of butanone was 18.35%, and the selectivity of butanone oxime was 90.54%.

[0122] Comparative Example 3

[0123] A preparation method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are:

[0124] 15g of nickel-doped titanium silicon molecular sieve catalyst and 80g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 94g of ammonia water and 140g of hydrogen peroxide were added. The reaction temperature was 80°C and the reaction time was 5h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; it is characterized in that a nickel-doped titanium silicon molecular sieve catalyst is used in the catalytic ammoximation reaction.

[0125] The nickel-doped nickel-doped titanium silicon molecular sieve catalyst is prepared as follows:

[0126] S1: In a quartz tube fixed bed reactor, 30g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 10% dilute hydrochloric acid at 700°C to create vacancies in the framework, and then 50g of TiCl4 is introduced into the reactor with N2, and isomorphous substitution reaction is carried out at 400°C for 1h, and titanium is inserted. After cooling and drying, a nickel-doped titanium silicon molecular sieve catalyst is obtained.

[0127] S2: 15g nickel-doped titanium silicon molecular sieve catalyst, 3g aminosilane, 100g DMF, stirred at 50°C for 120 minutes,

[0128] S3: Add 1.5 g of nickel acrylate, 0.02 g of 4-propylenethiosemicarbazide, and 0.1 g of an organic base, stir at 60° C. for 120 minutes, filter, and dry to obtain a nickel-doped nickel-doped titanium silicon molecular sieve catalyst;

[0129] The mass fraction of the ammonia water is 25%.

[0130] The mass fraction of the hydrogen peroxide is 35%.

[0131] The hydrogen peroxide and ammonia water are fed in a continuous manner.

[0132] The high-silicon or full-silicon zeolite molecular sieve is ZSM-5.

[0133] The N2 and TiCl4 mixture enters from the bottom of the reactor.

[0134] The aminosilane coupling agent is KH550.

[0135] The organic base is ethanolamine.

[0136] In this experiment, the conversion rate of butanone was 45%, and the selectivity of butanone oxime was 95.12%.

Claims

1. A method for producing butanone oxime using nickel-doped titanium silicon molecular sieve, the operating steps of which are: 10g of nickel-doped titanium silicon molecular sieve catalyst and 64g of butanone were stirred and mixed evenly, and then the feed liquid was added to the reactor, and then 70g of ammonia water and 103g of hydrogen peroxide were added. The reaction temperature was 70°C and the reaction time was 3h to generate a reaction liquid mixture; the mixture was sent to a separator for stratification into organic and inorganic phases, and the upper organic phase was the product butanone oxime; The nickel-doped titanium silicon molecular sieve catalyst is prepared by the following method: S1: In a quartz tube fixed bed reactor, 36g of high silicon or full silicon zeolite molecular sieve is first dealuminated with 16% dilute hydrochloric acid at 830°C to generate vacancies in the framework, and then 56g of TiCl4 is introduced into the reactor with N2, and an isomorphous substitution reaction is carried out at 600°C for 3h, followed by titanium insertion, cooling and drying to obtain a titanium silicon molecular sieve catalyst; S2: 22g titanium silicon molecular sieve catalyst, 5g aminosilane, 116g DMF, stirred at 68°C for 140 minutes, S3: Add 3 g of nickel acrylate, 0.6 g of 4-propylenethiosemicarbazide, and 1.8 g of an organic base, stir at 66° C. for 150 minutes, filter, and dry to obtain a nickel-doped titanium silicon molecular sieve catalyst; The mass fraction of the ammonia water is 25%; The mass fraction of the hydrogen peroxide is 35%; The hydrogen peroxide and ammonia water are fed in a continuous manner; The high-silicon or full-silicon zeolite molecular sieve is ZSM-5; The N2 and TiCl4 mixture enters from the bottom of the reactor; The aminosilane coupling agent is KH551; The organic base is triethanolamine.

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