CN108997123B - Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene - Google Patents
Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene Download PDFInfo
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- CN108997123B CN108997123B CN201811056985.4A CN201811056985A CN108997123B CN 108997123 B CN108997123 B CN 108997123B CN 201811056985 A CN201811056985 A CN 201811056985A CN 108997123 B CN108997123 B CN 108997123B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
The invention provides a method for synthesizing phthalate by using catalytic oxidation products of o-xylene or naphthalene, which is characterized by comprising the following steps: the method comprises preparing phthalic anhydride, synthesizing phthalic acid ester; the phthalate ester synthesis comprises the steps of feeding, dropwise adding n-butyl alcohol and carrying out negative pressure reaction. The method for synthesizing the phthalate ester has low reaction temperature which is below 105 ℃. According to the method for synthesizing the phthalic acid ester, the using amount of the alcohol is low, and the molar using amount of the alcohol is 2.05 times that of phthalic anhydride; the method for synthesizing the phthalate has high reaction yield, and the reaction yield is more than 99.4%; after the application of the catalyst for 10 times, the yield can be kept at 99.0 percent.
Description
Technical Field
The invention relates to a method for synthesizing phthalate by using catalytic oxidation products of o-xylene or naphthalene, belonging to the technical field of chemical synthesis.
Background
Phthalic anhydride is an important basic organic chemical raw material, which is obtained by catalytic oxidation of o-xylene or naphthalene, namely phthalic anhydride is a catalytic oxidation product of o-xylene or naphthalene; the method for preparing phthalic anhydride by using o-xylene and/or naphthalene as raw materials through fixed bed catalytic oxidation generally adopts a V-Ti type catalyst, namely vanadium pentoxide and titanium dioxide as catalytic active substances, at least one compound selected from alkali metals, Sb, P, Nb, Ag and the like is added as a cocatalyst, and the catalytic active substances are coated on an inert non-porous carrier by using a non-porous inert carrier material in a thin layer shape of 0.02-2 mm usually.
Chinese patent CN101130535A discloses a method for preparing phthalic anhydride, which uses o-xylene and naphthalene as raw materials, adopts a two-stage, three-stage bed or four-stage bed V-Ti type catalyst, the catalyst covers a carrier with a catalytic active substance containing vanadium pentoxide and titanium dioxide, and adds compounds of alkali metal, Sb, P and Nb as a cocatalyst. When the two-stage bed catalyst is used, the yield of phthalic anhydride can only reach 113%; when three-stage or four-stage bed catalysts are used, the phthalic anhydride yield can reach up to 115%; however, the number of stages of the bed catalyst used is large, the cost is high, and the operation is complicated.
Phthalates are a class of plasticizer products that function as softening agents. It is commonly used in hundreds of products such as toys, food packaging materials, medical blood bags and hoses, vinyl floors and wallpaper, detergents, lubricating oils, personal care products, and the like.
The synthesis of phthalic acid ester is mainly prepared by esterification of phthalic anhydride and corresponding alcohol, the catalyst used in the industry at present is mainly concentrated sulfuric acid, the reaction temperature is generally 140-160 ℃, the catalytic effect is good, but the concentrated sulfuric acid is dangerous to operate and has certain corrosivity to equipment; besides concentrated sulfuric acid, other liquid acids, salts, heteropoly acids, solid super acids and the like are used, but the catalysts have the obvious defects of low catalytic activity, high required reaction temperature which is generally more than 200 ℃, low yield of the prepared phthalic acid ester and the like, and are difficult to realize industrialization.
Patent CN104592030A discloses a method for synthesizing phthalate ester compounds, which uses weak acid as main catalyst, and other auxiliary catalysts to synthesize phthalate ester compounds, wherein the main catalyst is weak acid or salt. The weak acid is sulfamic acid, p-toluenesulfonic acid or oxalic acid; the salt is sodium bisulfate, potassium bisulfate, ferric chloride, stannic chloride and aluminum chloride; the cocatalyst is a nitrogen group element compound or polyethylene glycol; the nitrogen compound is quaternary phosphonium salt, arsenic crown ether, quaternary ammonium salt, tetrabutylammonium bromide or methyl trioctyl ammonium chloride. The reaction process is that after the materials are added, the reactor is ensured to be sealed, the temperature is raised to boiling, the reaction is carried out for 0.5 to 2 hours, and the product is obtained by rectification, the yield is 98.3 percent at most, and the required reaction temperature is above 117.7 ℃.
Patent CN103435487A discloses a method for preparing phthalate, which uses phthalic anhydride and monohydric aliphatic alcohol as raw materials, and performs esterification reaction under the action of non-acidic catalyst; the non-acidic catalyst is one of stannous oxide or stannous chloride. The technology firstly reacts for 1 hour at the temperature of 130-; the reaction temperature was high and the amount of alcohol added was 3.0 to 3.5 times (molar ratio) that of phthalic anhydride, and the alcohol was added in excess.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for synthesizing phthalate by using a catalytic oxidation product of o-xylene or naphthalene, which aims to realize the following purposes:
(1) a step of synthesizing phthalate, which is to reduce the reaction temperature;
(2) a step of synthesizing phthalate ester, which reduces the dosage of alcohol;
(3) the phthalate ester is synthesized, so that the reaction yield is improved;
(4) and the step of synthesizing the intermediate phthalic anhydride reduces the number of loading sections of the catalyst in a fixed bed reactor, reduces side reactions in the oxidation process and improves the reaction yield.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for synthesizing a phthalate ester from the catalytic oxidation product of ortho-xylene or naphthalene, said method comprising preparing phthalic anhydride, synthesizing the phthalate ester; the phthalate ester synthesis comprises the steps of feeding, dropwise adding n-butyl alcohol and carrying out negative pressure reaction.
The following is a further improvement of the above technical solution:
the feeding is to add phthalic anhydride, a certain amount of n-butanol and a composite catalyst into a reactor, stir and mix, and then heat to 93-97 ℃.
Stirring, wherein the stirring speed is 1000r/min, and the stirring time is 15 minutes;
the temperature is preferably raised to 95 ℃.
And when the n-butanol is dropwise added, keeping the temperature in the reactor at 105 ℃ and the dropwise adding time of the n-butanol at 28-32 minutes.
The dropping time is preferably 30 minutes;
in the dropping process of the n-butyl alcohol, the reactor is intermittently stirred, the stirring is carried out for 5 minutes at the speed of 800r/min, the stirring is stopped for 1 minute, and the stirring is carried out circularly by taking the stirring as 1 period.
And (3) carrying out negative pressure reaction, adjusting the pressure of the reactor to 70-75Kpa after the dropwise addition is finished, and reacting for 29-33 minutes at the reaction temperature of 90-93 ℃.
The reaction temperature is preferably 90 ℃ and the reaction time is preferably 30 minutes.
The adding amount of the n-butyl alcohol is 45-50wt% of the total amount of the n-butyl alcohol; the molar ratio of phthalic anhydride to the total amount of n-butanol is as follows: 1:2.05.
The addition amount of the composite catalyst is 0.8-1.2% of the weight of phthalic anhydride.
The composite catalyst comprises the following components in parts by weight: 5 parts of phosphotungstic acid, 1 part of potassium tetranitroplatinate and 2 parts of molybdenum acetylacetonate.
The preparation of phthalic anhydride comprises the steps of preparing a catalyst 1, preparing a catalyst 2 and reacting.
In the catalyst 1, active substances are triisopropoxytrianadate, bismuth molybdate, isopropyl titanate and tin oxide, the content of the active substances on a carrier is 9-11%, and the mass ratio of the triisopropoxytrianadate, the bismuth molybdate, the isopropyl titanate and the tin oxide is as follows: 78-83:9-11:590-605:6.5-7.5.
The preparation method of the catalyst 1 comprises the following steps: preparing triisopropoxytrianadate, bismuth molybdate and formamide into a solution 1, mixing and emulsifying the solution 1 with isopropyl titanate and tin oxide to obtain a uniform suspension, spraying the suspension on a carrier aluminum silicate until the content of active substances on the carrier reaches 9-11%, and preparing a catalyst 1;
in the solution 1, the concentrations of vanadium isopropoxide and bismuth molybdate are 30-33%.
In the catalyst 2, active substances are ammonium metavanadate, sodium molybdate, isopropyl titanate and tin oxide, and the content of the active substances on the carrier is 12.5-13.5%; the mass ratio of the ammonium metavanadate to the sodium molybdate to the isopropyl titanate to the tin oxide is 95-105:7-9: 595-610: 17-19.
The preparation method of the catalyst 2 comprises the steps of preparing ammonium metavanadate, sodium molybdate and formamide into a solution 2, mixing and emulsifying the solution 2 with isopropyl titanate and tin oxide into a uniform suspension, spraying the suspension on a carrier aluminum silicate until the content of active substances on the carrier reaches 12.5-13.5%, and preparing the catalyst 2;
in the solution 2, the concentrations of ammonium metavanadate and sodium molybdate are 34-36%;
the reaction, air sample introduction flow rate is 5Nm3H, ortho-xylene concentration 102g/Nm3The reaction temperature was 330 ℃.
The reaction is carried out in a fixed bed reactor, in the fixed bed reactor with the inner diameter of 30mm and the tube length of 3500mm, the upper section bed layer is filled with a catalyst 1, the filling height is 1500mm, the lower section bed layer is filled with a catalyst 2, the filling height is 1000mm, two ends of the upper section bed layer are respectively sealed by quartz sand, and the length of the two ends of the upper section bed layer is 500 mm.
Through the technical scheme, the invention can realize the following beneficial effects:
(1) the method for synthesizing the phthalate ester has low reaction temperature which is below 105 ℃.
(2) The method for synthesizing the phthalic acid ester has low alcohol dosage, and the molar dosage of the alcohol is 2.05 times of that of phthalic anhydride.
(3) The method for synthesizing the phthalate has high reaction yield, and the reaction yield is more than 99.4%; after the application of the catalyst for 10 times, the yield can be kept at 99.0 percent.
(4) In the step of preparing the intermediate product phthalic anhydride, a continuous catalysis mode is adopted, a composite catalyst is adopted, side reactions are few in the oxidation process, the product yield is high, and the yield (calculated by o-xylene) is 118-118.5%.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and the described embodiments are some embodiments, but not all embodiments, of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 Synthesis of phthalate esters from the catalytic Oxidation products of ortho-xylene or naphthalene
The method comprises the following steps:
step 1 preparation of phthalic anhydride
(1) Preparation of catalyst 1
80g of vanadium isopropoxide, 10g of bismuth molybdate and 200g of formamide are prepared into a solution 1, the solution 1, 600g of isopropyl titanate and 7g of tin oxide are mixed and emulsified into a uniform suspension, and the suspension is sprayed on a carrier of aluminum silicate until the content of active substances on the carrier reaches 10%, so that the catalyst 1 is prepared.
(2) Preparation of catalyst 2
100g of ammonium metavanadate, 8g of sodium molybdate and 200g of formamide are prepared into a solution 2, and 600g of formamide is added
Isopropyl titanate and 18g of tin oxide are mixed and emulsified into uniform suspension, and the suspension is sprayed on carrier aluminum silicate until the content of active substances on the carrier reaches 13 percent to prepare the catalyst 2.
(3) Oxidation reaction
Preparing phthalic anhydride in a fixed bed reactor, wherein in the fixed bed reactor with the inner diameter of 30mm and the tube length of 3500mm, the upper bed layer is filled with a catalyst 1 with the filling height of 1500mm, the lower bed layer is filled with a catalyst 2 with the filling height of 1000mm, two ends of the bed layer are respectively sealed by quartz sand, and the length of the seals at the two ends is 500 mm; the reaction product is collected in a trapping device, the molten salt which forcibly flows in a circulating way is adopted outside the reactor as a heat exchange body, and the reaction heat is led out by the molten salt.
In the fixed bed reactor, the air sample injection flow is 5Nm3H, ortho-xylene concentration 102g/Nm3Air and o-xylene flow into a reactor to react, the salt bath temperature is 355 ℃, and the circulating amount of the molten salt is 5000m3And h, the yield of the phthalic anhydride (calculated by o-xylene) at the outlet of the solid bed reactor is 118%, and phthalic anhydride solid is obtained after cooling.
The phthalic anhydride was reacted with naphthalene in place of o-xylene, and the yield of phthalic anhydride (in terms of naphthalene) was 118.5%.
Step 2, synthesizing phthalic acid ester
(1) Charging of
Adding 50Kg of phthalic anhydride, 25Kg of n-butanol and 0.5Kg of composite catalyst into a reactor, stirring for 15 minutes at the speed of 1000r/min, and then heating to 95 ℃;
the composite catalyst comprises the following components in parts by weight: 5 parts of phosphotungstic acid, 1 part of potassium tetranitroplatinate and 2 parts of molybdenum acetylacetonate.
(2) Dropwise adding n-butanol
Dropwise adding 26.25kg of n-butanol into the reactor, wherein when the n-butanol is dropwise added, the temperature in the reactor is kept at 105 ℃, and the dropwise adding time of the n-butanol is 30 minutes; in the dropping process of the n-butyl alcohol, the reactor is intermittently stirred, the stirring is carried out for 5 minutes at the speed of 800r/min, the stirring is stopped for 1 minute, and the stirring is carried out circularly by taking the stirring as 1 period.
The molar ratio of the total amount of n-butanol to phthalic anhydride in step (1) and step (2) was 2.05: 1.
(3) Negative pressure reaction
After the completion of the dropwise addition, the pressure in the reactor was adjusted to 72Kpa at a reaction temperature of 90 ℃ for 30 minutes.
(4) Rectification
Cooling the reactor to below 40 ℃, and rectifying to obtain a dibutyl phthalate product, wherein the yield is 99.4 percent based on phthalic anhydride.
EXAMPLE 2 catalyst application test
Rectifying the reaction product of the embodiment 1 to obtain a dibutyl phthalate product, and rectifying and dehydrating; the residual component is the catalyst (containing a small amount of unreacted phthalic anhydride and n-butanol), the catalyst is applied to the synthesis reaction of the next batch for 10 times, and the yield result of the dibutyl phthalate is as follows:
the catalytic oxidation product of o-xylene or naphthalene according to the invention is phthalic anhydride.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for synthesizing phthalate ester by using catalytic oxidation products of ortho-xylene or naphthalene is characterized in that: the method comprises preparing phthalic anhydride, synthesizing phthalic acid ester; the phthalate ester synthesis comprises the steps of feeding, dropwise adding n-butyl alcohol and carrying out negative pressure reaction;
the composite catalyst is added into the synthesized phthalic acid ester, and the adding amount of the composite catalyst is 0.8-1.2% of the weight of phthalic anhydride; the composite catalyst comprises the following components in parts by weight: 5 parts of phosphotungstic acid, 1 part of potassium tetranitroplatinate and 2 parts of molybdenum acetylacetonate.
2. The process of claim 1 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: the feeding is to add phthalic anhydride, a certain amount of n-butanol and a composite catalyst into a reactor, stir and mix, and then heat to 93-97 ℃.
3. The process of claim 1 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: and when the n-butanol is dropwise added, keeping the temperature in the reactor at 105 ℃ and the dropwise adding time of the n-butanol at 28-32 minutes.
4. The process of claim 1 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: and (3) carrying out negative pressure reaction, after the dropwise addition is finished, adjusting the pressure of the reactor to 70-75KPa, controlling the reaction temperature to be 90-93 ℃, and reacting for 29-33 minutes.
5. The process of claim 2 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: the adding amount of the n-butyl alcohol is 45-50wt% of the total amount of the n-butyl alcohol; the molar ratio of phthalic anhydride to the total amount of n-butanol is as follows: 1:2.05.
6. The process of claim 1 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: the preparation of phthalic anhydride comprises the steps of preparing a catalyst 1, preparing a catalyst 2 and reacting.
7. The method of claim 6 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: in the catalyst 1, active substances are triisopropoxytrianadate, bismuth molybdate, isopropyl titanate and tin oxide, the content of the active substances on a carrier is 9-11%, and the mass ratio of the triisopropoxytrianadate, the bismuth molybdate, the isopropyl titanate and the tin oxide is as follows: 78-83:9-11:590-605:6.5-7.5.
8. The method of claim 6 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: in the catalyst 2, active substances are ammonium metavanadate, sodium molybdate, isopropyl titanate and tin oxide, and the content of the active substances on the carrier is 12.5-13.5%; the mass ratio of the ammonium metavanadate to the sodium molybdate to the isopropyl titanate to the tin oxide is 95-105:7-9: 595-610: 17-19.
9. The method of claim 6 for the synthesis of phthalates from the catalytic oxidation products of ortho-xylene or naphthalene, wherein: the reaction, air sample introduction flow rate is 5Nm3H, ortho-xylene concentration 102g/Nm3The reaction temperature was 330 ℃.
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Citations (6)
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| CN1030571A (en) * | 1987-04-10 | 1989-01-25 | 新日铁化学株式会社 | The preparation method of Tetra hydro Phthalic anhydride |
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| CN1291180A (en) * | 1998-02-16 | 2001-04-11 | 三菱化学株式会社 | Process for producing ester |
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2018
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| JPH06157405A (en) * | 1992-11-20 | 1994-06-03 | Sekisui Chem Co Ltd | Production of ester |
| CN1237951A (en) * | 1996-10-23 | 1999-12-08 | 新日铁化学标式会社 | Gas-phase oxidization process and process for preparation of phthalic anhydride |
| CN1291180A (en) * | 1998-02-16 | 2001-04-11 | 三菱化学株式会社 | Process for producing ester |
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