CN112079704B - Preparation method of butyl butyrate and butyric acid - Google Patents
Preparation method of butyl butyrate and butyric acid Download PDFInfo
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Abstract
The invention discloses a preparation method of butyl butyrate and butyric acid, wherein the preparation method of the butyl butyrate comprises the following steps: preheating butanol, gasifying at a pressure of not less than 0.1MPa for 0.7hr ‑1 ‑1hr ‑1 With the catalyst Si at a flow rate of x Fe y V z O w Contacting, and condensing the generated mixed gas to obtain a mixed solution; wherein x is 0.20-0.35, y is 0.01-0.20, z is 0.01-0.05, w is 2x +1.5y +2.5 z; and rectifying and separating the mixed solution to obtain butyl butyrate. The invention adopts the silicon/iron/vanadium ferrite system to carry out the dehydrogenation oxidation reaction of the butanol to prepare the butyl butyrate, has no waste acid, no waste water discharge and no pollution to the environment, and under the condition that the selectivity of the target product is obviously basically consistent, the reaction conversion rate is increased to a certain extent, the conversion rate of the butanol is more than 68mol percent, and the selectivity of the butyl butyrate is more than 75mol percent.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of butyl butyrate and butyric acid.
Background
Butyric acid is an important synthetic perfume and a raw material of other fine chemical products, and is mainly used for synthesizing butyrate and cellulose butyrate. The butyrate has different fruit flavors and can be widely applied to the fields of essence, food additives, medicines and the like. Cellulose butyrate has excellent heat resistance, light resistance and moisture resistance, and simultaneously has good forming and stability, and is excellent coating and molding. Can be used as flavoring agent in preparation of medicine, and also can be used as salt forming agent to increase solubility of medicine; in addition, the compound can also be used as a medical intermediate; wherein isobutyl isobutyrate is mainly used for modulating spices and essence and is the main component of pineapple essence; it is also an excellent organic solvent, dry paint remover, extractive distillation additive.
Further, isobutyric acid, isobutyrate ester, and isobutyric anhydride are important organic intermediates, and tetramethylcyclobutanediol, which is an essential raw material for synthesizing biodegradable polyesters having excellent properties, can be synthesized by a high-temperature cracking method or a low-temperature condensation method. Polyesters synthesized using tetramethylcyclobutanediol are highly transparent, high in use temperature, free of BPA, and materials can be used in medical applications and infant contact devices, thus having great market demand.
Patent CN1238327C discloses a method for synthesizing isobutyric acid by water oxidation and heterogeneous catalysis of isobutyraldehyde, which comprises the following steps: isobutyraldehyde and water are gasified respectively and then mixed to synthesize isobutyric acid by the action of a catalyst, the catalyst is a heterogeneous catalyst consisting of Cu, Zn, Al, Zr and an oxide of one or more elements selected from the rare earths La, Ce and Y, and the reaction temperature is 200-350 ℃. The disadvantage of this catalyst is its poor stability and, in general, the activity drops sharply with a few reactions.
Patent CN1296132C uses a zirconium based catalyst for the synthesis of isobutyric acid. The zirconium-based catalyst consists of oxides of copper, zinc and zirconium and one or more rare earth elements of lanthanum, cerium, yttrium and the like, wherein the content of each component in terms of metal is 5-40% of Cu, 0-10% of Zn, 50-90% of Zr and 1-10% of Re, and the catalyst is used in a method for producing isobutyric acid through water oxidation synthesis reaction of isobutyraldehyde; the stability of the catalyst is partially improved with respect to the technique of patent CN 1238327C.
Patent CN1191227C adopts the following workThe method comprises the following steps: gasifying butanol in the presence of hydrogen, passing through a reactor at 200-300 ℃, and reacting with a catalyst expressed as Cu a ZnCr b M c O x Contacting the catalyst, separating and collecting butyl butyrate. M is an element selected from group IVB, preferably Ti and Zr. The catalytic system can be directly dehydrogenated from butanol to butyl butyrate. But the proportion of Cu has a relatively large influence on the selectivity of butyl butyrate. Therefore, in the process of preparing the catalyst, the conditions required for the preparation are relatively high, and at the same time, the conversion rate of the overall reaction is not too high.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of butyl butyrate, which is a composite metal catalyst consisting of silicon base and metal elements such as Fe, V and the like, wherein the catalyst has better stability and catalytic performance in the process of synthesizing butanol by dehydrogenation.
The invention also provides a method for preparing butyric acid by using the butyl butyrate prepared by the preparation method.
The invention is realized by adopting the following technical scheme:
a preparation method of butyl butyrate comprises the following preparation steps:
s1: preheating butanol, gasifying at a pressure of not less than 0.1MPa for 0.7hr -1 -1hr -1 With the catalyst Si at a flow rate of x Fe y V z O w Contacting, and condensing the generated mixed gas to obtain a mixed solution; wherein x is 0.20-0.35, y is 0.01-0.20, z is 0.01-0.05, w is 2x +1.5y +2.5 z;
s2: and (3) rectifying and separating the mixed solution to obtain butyl butyrate.
Further, the catalyst Si x Fe y V z O w Silicate ester, ferric chloride and vanadium chloride are mixed in a solvent to form a homogeneous solution, the homogeneous solution is stood, the pH value of the solution is adjusted, and the solution is obtained by stirring, filtering, washing, drying and calcining.
Further, the mole ratio of silicate ester, ferric chloride and vanadium chloride is 2-11: 0.8-1.6: 0.5-0.9.
Further, the catalyst Si x Fe y V z O w The preparation method comprises the following steps:
(1) dissolving quaternary ammonium salt cationic surfactant in deionized water at 35-40 deg.c, and adding hydrochloric acid to form mixed solvent;
(2) adding silicate ester into the mixed solvent, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding ferric chloride and vanadium chloride, and continuously stirring for 24 hours to obtain a homogeneous solution;
(3) adding ammonia water into the homogeneous solution, adjusting the pH value of the solution to be 8-10, adding methanol, stirring, and filtering to obtain a precipitate solid;
(4) washing the precipitated solid with water and methanol in sequence, drying for 4h in a blast oven at 100 ℃, calcining for 16h-24h in a tubular furnace at 400-450 ℃, and finally pressing to obtain the catalyst Si x Fe y V z O w 。
Further, the quaternary ammonium salt type cationic surfactant is one of cetyl trimethyl ammonium bromide and tetrabutyl ammonium bromide.
Further, the molar ratio of the quaternary ammonium salt type cationic surfactant to the silicate is 0.5-3.5: 2-11.
Further, the catalyst Si x Fe y V z O w An activation step is required before use.
Further, the activating step comprises: catalyst Si x Fe y V z O w Putting the mixture into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.1MPa-0.5MPa of hydrogen and the activation temperature of 200-300 ℃.
Furthermore, the preheating temperature of the butanol is 280-300 ℃, the carrier gas for adjusting the pressure of the reaction system is hydrogen, the pressure of the reaction system is controlled to be 0.1-1 MPa, and the ratio of the butanol to the hydrogen is 0.1-0.5.
The invention also provides butyric acid, which comprises the following preparation steps: preparing butyl butyrate by the preparation process of claims 1 to 9; and (3) carrying out alkaline hydrolysis and then separating the butyl butyrate to obtain the butyric acid.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts silicon/iron/vanadium ferrite system to carry out dehydrogenation oxidation reaction of butanol to prepare butyl butyrate, has no waste acid, no waste water discharge and no pollution to environment, and compared with the butyl butyrate process in the prior art, under the condition that the target product selectivity is obviously and basically consistent, the reaction conversion rate of the preparation method is improved to a certain extent, the conversion rate of butanol is more than 68 mol%, and the selectivity of butyl butyrate is more than 75 mol%.
The invention is a composite metal catalyst composed of silicon base and Fe, V and other metal elements, and the catalyst does not use Cu, Zr and other metal elements, and has better stability and catalytic performance in the process of butanol dehydrogenation synthesis.
The preparation method is suitable for preparing C2-C12 ester or C1-C6 acid by using C1-C6 alcohol as a raw material.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, various embodiments or technical features described below may be arbitrarily combined to form a new embodiment.
The invention provides a preparation method of butyl butyrate, which comprises the following preparation steps:
s1: preheating butanol for 0.7hr at a pressure of not less than 0.1MPa -1 -1hr -1 With the catalyst Si at a flow rate of x Fe y V z O w Contacting, and condensing the generated mixed gas to obtain a mixed solution; wherein x is 0.20-0.35, y is 0.01-0.20, z is 0.01-0.05, w is 2x +1.5y +2.5 z;
s2: and rectifying and separating the mixed solution to obtain butyl butyrate.
Wherein the butanol is one of butanol isomers such as but not limited to n-butanol, isobutanol, sec-butanol, tert-butanol, etc., and butyl butyrate of corresponding butanol isomer can be synthesized, such as n-butyl butyrateButyl ester, isobutyl isobutyrate, sec-butyl sec-butyrate and tert-butyl tert-butyrate. The catalyst Si x Fe y V z O w Silicate ester, ferric chloride and vanadium chloride are mixed in a solvent to form a homogeneous solution, the homogeneous solution is stood, the pH value of the solution is adjusted, and the solution is obtained by stirring, filtering, washing, drying and calcining. Catalyst Si x Fe y V z O w The catalyst is a composite metal catalyst based on the gas-solid reaction characteristic of butanol and silicon base, metal elements such as Cu, Zr and the like are not used in the catalyst, metal elements such as Fe, V and the like are used, and a sintering method is adopted to obtain the solid catalyst. In one embodiment, the mole ratio of silicate ester, ferric chloride and vanadium chloride is 2-11: 0.8-1.6: 0.5-0.9. The silicate is, but not limited to, one of ethyl silicate, methyl silicate, propyl silicate, and in this embodiment, the silicate is ethyl orthosilicate. In another embodiment, ferric chloride may also be replaced with ferric nitrate.
Specifically, the catalyst Si x Fe y V z O w The preparation method comprises the following steps:
(1) dissolving quaternary ammonium salt cationic surfactant in deionized water at 35-40 deg.c, and adding hydrochloric acid to form mixed solvent;
(2) adding silicate ester into the mixed solvent, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding ferric chloride and vanadium chloride, and continuously stirring for 24 hours to obtain a homogeneous solution;
(3) adding ammonia water into the homogeneous solution, adjusting the pH value of the solution to 8-10, adding methanol, stirring, and filtering to obtain a precipitate solid;
(4) washing the precipitated solid with water and methanol in sequence, drying for 4h in a forced air oven at 100 ℃, calcining for 16h-24h in a tubular furnace at 400-450 ℃, and finally pressing to obtain the catalyst Si x Fe y V z O w 。
Wherein, the quaternary ammonium salt cationic surfactant is one of cetyl trimethyl ammonium bromide and tetrabutyl ammonium bromide; the molar ratio of the quaternary ammonium salt cationic surfactant to the silicate ester is 0.5-3.5: 2-11. In step (4), the calcination is sintering in an oxygen atmosphere.
The catalyst Si x Fe y V z O w Before use, the preparation needs to be subjected to an activation step, wherein the activation step comprises the following steps: catalyst Si x Fe y V z O w Putting the mixture into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.1MPa-0.5MPa of hydrogen and the activation temperature of 200-300 ℃.
Preferably, the preheating temperature of the butanol is 280-300 ℃, the carrier gas for adjusting the pressure of the reaction system is hydrogen, the pressure of the reaction system is controlled to be 0.1-1 MPa, and the ratio of the butanol to the hydrogen is 0.1-0.5.
The preparation method adopts the silicon/iron/vanadium ferrite system to carry out dehydrogenation oxidation reaction of the butanol to prepare the butyl butyrate, has no waste acid, no waste water discharge and no pollution to the environment, and compared with the butyl butyrate process in the prior art, under the condition that the target product selectivity is obviously and basically consistent, the reaction conversion rate of the preparation method is improved, the conversion rate of the butanol is more than 68mol percent, and the selectivity of the butyl butyrate is more than 75mol percent.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1
Preparation of the catalyst:
dissolving 2g of hexadecyl trimethyl ammonium bromide in 100mL of deionized water at 35-40 ℃, adding 100mL of hydrochloric acid (2M), adding 5.5g of ethyl orthosilicate, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding 2.4g of ferric chloride and 1.2g of vanadium chloride, and continuously stirring for 24 hours; adjusting the pH value of the solution to 8-10 by using ammonia water, adding 100mL of methanol, stirring, and filtering to obtain a precipitate solid; and then washing the precipitated solid with 20mL of water and 20mL of methanol in sequence, drying the solid in a blast oven at 100 ℃ for 4 hours, and calcining the solid in a tube furnace at 450 ℃ for 24 hours to prepare a precatalyst C-1: si 0.300 Fe 0.025 V 0.011 O 0.658 And finally pressingTo obtain a shaped precatalyst C-1: si 0.300 Fe 0.025 V 0.011 O 0.658 。
Activation of the catalyst:
and (3) loading the pre-catalyst C-1 into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.5MPa of hydrogen and the activation temperature of 250 ℃ to obtain the activated catalyst C-1.
Preparation of butyl butyrate:
preheating isobutanol/hydrogen at a ratio of 0.3 for gasification at 290 deg.C under 0.5MPa for 0.8hr -1 The reaction solution was collected and measured by a gas chromatograph using a packed column PEG20000, the conversion of isobutyl alcohol was 72 mol% and the selectivity of isobutyl isobutyrate was 81 mol%.
Example 2
Preparation of the catalyst:
dissolving 4.2g of hexadecyl trimethyl ammonium bromide in 100mL of deionized water at 35-40 ℃, adding 100mL of hydrochloric acid (2M), adding 8.1g of tetraethoxysilane, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding 1.3g of ferric chloride and 0.9g of vanadium chloride, and continuously stirring for 24 hours; adjusting the pH value of the solution to 8-10 by using ammonia water, adding 100mL of methanol, stirring, and filtering to obtain a precipitate solid; and then washing the precipitated solid with 20mL of water and 20mL of methanol in sequence, drying the solid in a blast oven at 100 ℃ for 4 hours, and calcining the solid in a tubular furnace at 500 ℃ for 16 hours to prepare a precatalyst C-2: si 0.213 Fe 0.076 V 0.048 O 0.660 And finally pressing to obtain the formed precatalyst C-2: si 0.213 Fe 0.076 V 0.048 O 0.660 。
Activation of the catalyst:
and (3) loading the pre-catalyst C-2 into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.5MPa of hydrogen and the activation temperature of 250 ℃ to obtain the activated catalyst C-2.
Preparation of butyl butyrate:
preheating isobutanol/hydrogen gas with the proportion of 0.2 for gasification, and reacting at the preheating temperature of 300 DEG CThe pressure is 0.4MPa and 0.7hr -1 The reaction solution was collected and measured by a gas chromatograph using a packed column PEG20000, the conversion of isobutanol was 69 mol%, and the selectivity of isobutyl isobutyrate was 78 mol%.
Example 3
Preparation of the catalyst:
dissolving 6.5g of tetrabutylammonium bromide in 120mL of deionized water at 35-40 ℃, adding 120mL of hydrochloric acid (2M), adding 12.3g of tetraethoxysilane, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding 2.5g of ferric chloride and 1.1g of vanadium chloride, and continuously stirring for 24 hours; adjusting the pH value of the solution to 8-10 by using ammonia water, adding 100mL of methanol, stirring, and filtering to obtain a precipitate solid; and then washing the precipitated solid with 20mL of water and 20mL of methanol in sequence, drying for 4 hours in a blast oven at 100 ℃, and calcining for 24 hours in a tube furnace at 450 ℃ to prepare a precatalyst C-3: si 0.221 Fe 0.088 V 0.033 O 0.657 And finally pressing to obtain the formed precatalyst C-3: si 0.221 Fe 0.088 V 0.033 O 0.657 。
Activation of the catalyst:
and (3) loading the pre-catalyst C-3 into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.5MPa of hydrogen and the activation temperature of 250 ℃ to obtain the activated catalyst C-3.
Preparation of butyl butyrate:
preheating isobutanol/hydrogen at a ratio of 0.4 for gasification at 300 deg.C under a pressure of 0.5MPa for 1.0hr -1 The reaction solution is collected and measured by a gas chromatograph of a packed column PEG20000, the conversion rate of the isobutyl alcohol is 68 mol%, and the selectivity of the isobutyl isobutyrate is 80 mol%.
Example 4
Preparation of the catalyst:
dissolving 10g tetrabutylammonium bromide in 150mL deionized water at 35-40 deg.C, adding 150mL hydrochloric acid (2M), adding 21.5g ethyl orthosilicate, stirring vigorously for over 24 hr, standing for 24 hr, adding 2.5g ferric chlorideAnd 1.3g of vanadium chloride, and continuously stirring for 24 hours; adjusting the pH value of the solution to 8-10 by using ammonia water, adding 100mL of methanol, stirring, and filtering to obtain a precipitate solid; and then washing the precipitated solid with 20mL of water and 20mL of methanol in sequence, drying for 4 hours in a blast oven at 100 ℃, and calcining for 24 hours in a tubular furnace at 500 ℃ to prepare a precatalyst C-4: si 0.265 Fe 0.049 V 0.023 O 0.661 And finally pressing to obtain the formed precatalyst C-4: si 0.265 Fe 0.049 V 0.023 O 0.661 。
Activation of the catalyst:
and (3) loading the pre-catalyst C-4 into a fixed bed catalyst evaluation device, and activating for 8 hours under the conditions of 0.5MPa of hydrogen and the activation temperature of 250 ℃ to obtain the activated catalyst C-4.
Preparation of butyl butyrate:
preheating isobutanol/hydrogen at a ratio of 0.2 for gasification at 290 deg.C under 0.5MPa for 0.9hr -1 The reaction solution was collected and measured by a gas chromatograph using a packed column PEG20000, the conversion of isobutanol was 73 mol%, and the selectivity of isobutyl isobutyrate was 75 mol%.
In the above embodiments, each material is not limited to the above-mentioned components, and each material may also be other single components described in the present invention, for example, methyl silicate, propyl silicate instead of ethyl orthosilicate, n-butanol, isobutanol, sec-butanol, tert-butanol instead of isobutanol, and the like, and the content of each material is not limited to the above-mentioned content, and the content of each material may also be a combination of the contents of other components described in the present invention, and will not be described again.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (8)
1. The preparation method of butyl butyrate is characterized by comprising the following preparation steps of:
s1: preheating butanol, gasifying at a pressure of not less than 0.1MPa for 0.7hr -1 -1hr -1 Under the condition of the flow rate of the mixed gas, the mixed gas is contacted with a catalyst SixFeyVzOw, and the generated mixed gas is condensed to obtain a mixed liquid; wherein x is 0.20-0.35, y is 0.01-0.20, z is 0.01-0.05, w is 2x +1.5y +2.5 z;
s2: rectifying and separating the mixed solution to obtain butyl butyrate;
the catalyst SixFeyVzOw needs to be subjected to an activation step before being used;
in step S1, the preheating temperature of butanol is 280-300 ℃, the carrier gas for adjusting the pressure of the reaction system is hydrogen, and the ratio of butanol to hydrogen is 0.1-0.5.
2. The method for preparing butyl butyrate according to claim 1, wherein the catalyst SixFeyVzOw is prepared by mixing silicate, ferric chloride and vanadium chloride in a solvent to form a homogeneous solution, standing, adjusting the pH value of the solution, stirring, filtering, washing, drying and calcining.
3. The process for the preparation of butyl butyrate according to claim 2, characterized in that the molar ratio of silicate, ferric chloride and vanadium chloride is between 2 and 11: 0.8-1.6: 0.5-0.9.
4. The method for preparing butyl butyrate according to claim 2, wherein the catalyst SixFeyVzOw is prepared by the following method:
(1) dissolving quaternary ammonium salt cationic surfactant in deionized water at 35-40 deg.c, and adding hydrochloric acid to form mixed solvent;
(2) adding silicate ester into the mixed solvent, continuously and violently stirring for more than 24 hours, standing for 24 hours, then adding ferric chloride and vanadium chloride, and continuously stirring for 24 hours to obtain a homogeneous solution;
(3) adding ammonia water into the homogeneous solution, adjusting the pH value of the solution to be 8-10, adding methanol, stirring, and filtering to obtain a precipitate solid;
(4) washing the precipitated solid with water and methanol in sequence, drying the solid for 4 hours in a blast oven at 100 ℃, calcining the solid for 16 to 24 hours in a tubular furnace at 400 to 450 ℃, and finally pressing the solid to obtain the catalyst SixF eyVzOw.
5. The method of preparing butyl butyrate according to claim 4, wherein the quaternary ammonium salt cationic surfactant is one of cetyl trimethyl ammonium bromide and tetrabutyl ammonium bromide.
6. The process for the preparation of butyl butyrate according to claim 5, wherein the molar ratio of the quaternary ammonium salt cationic surfactant to the silicate ester is 0.5-3.5: 2-11.
7. The process for the preparation of butyl butyrate according to claim 1, characterized in that the activation step comprises: the catalyst SixFeyVzOw is put into a fixed bed catalyst evaluation device and activated for 8 hours under the conditions of 0.1MPa-0.5MPa of hydrogen and the activation temperature of 200-300 ℃.
8. The process for producing butyl butyrate according to claim 1, wherein in step S1, the reaction system pressure is controlled to 0.1MPa to 1 MPa.
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