CN108997123A - A method of with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene - Google Patents
A method of with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene Download PDFInfo
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- CN108997123A CN108997123A CN201811056985.4A CN201811056985A CN108997123A CN 108997123 A CN108997123 A CN 108997123A CN 201811056985 A CN201811056985 A CN 201811056985A CN 108997123 A CN108997123 A CN 108997123A
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- acid ester
- phthalic acid
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- xylene
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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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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of method with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene, it is characterised in that: the method, including prepare phthalic anhydride, synthesis phthalic acid ester；The synthesis phthalic acid ester, including feed, n-butanol, negative reaction is added dropwise.The method of synthesis phthalic acid ester of the present invention, reaction temperature is low, and reaction temperature is at 105 DEG C or less.The method of synthesis phthalic acid ester of the present invention, the dosage of alcohol is low, and the mole dosage of alcohol is 2.05 times of phthalic anhydride；The method of synthesis phthalic acid ester of the present invention, reaction yield is high, and reaction yield is greater than 99.4%；After applying 10 times, yield can also be maintained at 99.0%.
Description
Technical field
The present invention relates to a kind of methods with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene, belong to
Chemosynthesis technical field.
Background technique
Phthalic anhydride is a kind of important basic organic chemical industry raw material, is by ortho-xylene or naphthalene by catalysis
Oxidation obtains, i.e. phthalic anhydride, is the catalysis oxidation product of ortho-xylene or naphthalene；Using ortho-xylene and/or naphthalene as raw material
Fixed bed catalytic oxidation phthalic anhydride generally uses V-Ti type catalyst, i.e., is with vanadic anhydride and titanium dioxide
Catalytic active substance, and adding at least one compound selected from the compositions such as alkali metal, Sb, P, Nb, Ag is co-catalyst, with nothing
Catalytic active substance is usually 0.02-2 millimeters of lamelliform, coated on the non-porous carrier of inertia by hole inert support material
It is upper and prepare catalyst, catalyst used at present be in higher temperature, lesser gas feed amount and lower naphthalene or
Catalytic oxidation is carried out under ortho-xylene concentration, can reduce the generation of by-product, but used condition makes adjacent benzene two
The yield of formic anhydride is not high, prior art preparation phthalic anhydride, and yield (in terms of ortho-xylene) is up to 114%.
Chinese patent CN101130535A discloses a kind of preparation method of phthalic anhydride, is with ortho-xylene, naphthalene
Raw material, using two sections, three sections of beds or four sections of bed V-Ti type catalyst, the catalyst cover on carrier containing vanadic anhydride and
The catalytic active substance of titanium dioxide, and the compound of alkali metal, Sb, P, Nb are added as co-catalyst.The patent is using
When two sections of bed catalysts, the yield of phthalic anhydride is only capable of reaching 113%；When using three sections or four sections of bed catalysts, adjacent benzene
The yield of dicarboxylic acid anhydride could be up to 115%；But the number of segment of the bed catalyst used is more, and higher cost is cumbersome.
Phthalic acid ester is a kind of plasticizer product that can play emollescence.It is widely used in toy, food
Packaging material, medical blood bag and hundreds of products such as sebific duct, vinyl flooring and wallpaper, detergent, lubricating oil, personal-care supplies
In.
The synthesis of phthalic acid ester is mainly formed by phthalic anhydride with corresponding alcohol esterification, industrial at present
The catalyst used is mainly the concentrated sulfuric acid, and reaction temperature is generally 140-160 DEG C, good catalytic activity, but the concentrated sulfuric acid operates
Get up than relatively hazardous, and there is certain corrosivity to equipment；In addition to the concentrated sulfuric acid, there are also use other liquid acids, salt, miscellaneous more
Acid, solid super-strong acid etc., but that there are catalytic activity is lower for these catalyst, and required reaction temperature is higher, generally requires 200
DEG C or more, it is clearly disadvantageous that the phthalic acid ester yield of preparation is low etc., it is difficult to realize industrialization.
Patent CN104592030A discloses a kind of synthetic method of phthalate compound, using weak acid as main reminder
Agent, is aided with other co-catalysts synthesis phthalate compound, and major catalyst is weak acid or salt.The weak acid is ammonia
Base sulfonic acid, p-methyl benzenesulfonic acid or oxalic acid；The salt is sodium bisulfate, potassium acid sulfate, iron chloride, stannic chloride, aluminium chloride；Co-catalysis
Agent is nitrogen group element compound or polyethylene glycol；The nitrogen group element compound Wei quaternary alkylphosphonium salt, arsenic crown ether, quaternary ammonium salt, bromination
Tetrabutylammonium or methyl tricapryl ammonium chloride.Reaction process is, after charging, guarantees reactor sealing, is warming up to boiling, react
0.5-2 hours, rectifying obtained product, and yield is up to 98.3%, and the reaction temperature needed is at 117.7 DEG C or more.
Patent CN103435487A discloses a kind of preparation method of phthalic acid ester, with phthalic anhydride and unitary
Fatty alcohol is raw material, and esterification is carried out under the action of non-acidic catalyst；The non-acidic catalyst be stannous oxide or
One of stannous chloride.The technology is first reacted 1 hour at 130-160 DEG C, then is warming up to 170-210 DEG C of reaction 1-3 hours；Instead
Answer temperature higher, and the amount of its alcohol being added is 3.0-3.5 times (molar ratio) of phthalic anhydride, the alcohol of addition is excessive.
Summary of the invention
To solve the shortcomings of the prior art, the present invention provides a kind of with the conjunction of the catalysis oxidation product of ortho-xylene or naphthalene
At the method for phthalic acid ester, to realize following goal of the invention:
(1) phthalic acid ester step is synthesized, reaction temperature is reduced；
(2) phthalic acid ester step is synthesized, the dosage of alcohol is reduced；
(3) phthalic acid ester step is synthesized, reaction yield is improved；
(4) synthetic intermediate phthalic anhydride step reduces load number of segment of the catalyst in fixed bed reactors, reduces oxygen
Side reaction during change improves reaction yield.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A method of with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene, the method, including preparation
Phthalic anhydride, synthesis phthalic acid ester；The synthesis phthalic acid ester, including feed, n-butanol, negative pressure reverse is added dropwise
It answers.
It is further improvement to above-mentioned technical proposal below:
Phthalic anhydride, a certain amount of n-butanol, composite catalyst are added into reactor, is stirred, so for the charging
After be warming up to 93-97 DEG C.
The stirring, speed of agitator 1000r/min, mixing time are 15 minutes；
The heating is preferably warming up to 95 DEG C.
The dropwise addition n-butanol, when dropwise addition, keeping the temperature in reactor is 105 DEG C, and the time for adding of n-butanol is 28-
32 minutes.
The time for adding is preferably 30 minutes；
During n-butanol is added dropwise, intermittent stirring is carried out in reactor, is stirred 5 minutes, is stopped 1 minute with the rate of 800r/min,
As 1 period, circulation is carried out.
The negative reaction, is added dropwise, and adjusts the pressure of reactor to 70-75Kpa, reaction temperature is 90-93 DEG C, instead
It answers 29-33 minutes.
The reaction temperature is preferably 90 DEG C, and the reaction time is preferably 30 minutes.
The charging, the additional amount of n-butanol are the 45-50wt% of n-butanol total amount；The phthalic anhydride and positive fourth
The molar ratio of alcohol total amount are as follows: 1:2.05.
The composite catalyst additional amount is the 0.8-1.2% of phthalic anhydride weight.
The composite catalyst, in parts by weight, including following components: 5 parts of phosphotungstic acids, 1 part of tetranitro potassium platinate, 2 parts
Acetyl acetone.
It is described to prepare phthalic anhydride, including prepare catalyst 1, prepare catalyst 2, reaction.
The catalyst 1, active material is Triisopropoxyvanadium(V) oxide, bismuth molybdate, isopropyl titanate, tin oxide, on carrier
Activity substance content is 9-11%, the Triisopropoxyvanadium(V) oxide, bismuth molybdate, isopropyl titanate, tin oxide mass ratio are as follows: 78-
83:9-11:590-605:6.5-7.5。
The catalyst 1 the preparation method comprises the following steps: by Triisopropoxyvanadium(V) oxide, bismuth molybdate, formamide, solution 1 is configured to, with titanium
Isopropyl propionate, tin oxide mixing and emulsifying are uniform suspension, by suspension spray on carrier alumina silicate, until the work on carrier
Property content of material reaches 9-11%, and catalyst 1 is made；
In the solution 1, Triisopropoxyvanadium(V) oxide, bismuth molybdate concentration be 30-33%.
The catalyst 2, active material are ammonium metavanadate, sodium molybdate, isopropyl titanate, tin oxide, the activity on carrier
Content of material is 12.5-13.5%；The ammonium metavanadate, sodium molybdate, isopropyl titanate, tin oxide mass ratio be 95-105:7-
9:595-610:17-19.
The preparation method of the catalyst 2 is that ammonium metavanadate, sodium molybdate, formamide are configured to solution 2, different with metatitanic acid
Propyl ester, tin oxide mixing and emulsifying are uniform suspension, by suspension spray on carrier alumina silicate, until the active matter on carrier
Matter content reaches 12.5-13.5%, and catalyst 2 is made；
In the solution 2, ammonium metavanadate, sodium molybdate concentration be 34-36%；
The reaction, air sample introduction flow are 5Nm3/ h, ortho-xylene concentration are 102g/Nm3, reaction temperature is 330 DEG C.
The reaction carries out in fixed bed reactors, is 30mm in internal diameter, pipe range is the fixed bed reactors of 3500mm
In, upper section bed loading catalyst 1, filling height is 1500mm, and lower section bed loading catalyst 2, filling height is 1000mm,
Both ends are sealed with quartz sand respectively, and the length of sealing two ends is 500mm.
By above technical solution, the present invention may be implemented it is following the utility model has the advantages that
(1) method of synthesis phthalic acid ester of the present invention, reaction temperature is low, and reaction temperature is at 105 DEG C or less.
(2) method of synthesis phthalic acid ester of the present invention, the dosage of alcohol is low, and the mole dosage of alcohol is O-phthalic
2.05 times of acid anhydrides.
(3) method of synthesis phthalic acid ester of the present invention, reaction yield is high, and reaction yield is greater than 99.4%；It applies
After 10 times, yield can also be maintained at 99.0%.
(4) present invention prepares intermediate product phthalic anhydride step, by the way of continuous catalysis, using composite catalyzing
Agent, side reaction is few in oxidation process, and product yield is high, and yield (in terms of ortho-xylene) is 118-118.5%.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, and described embodiment is that a part of the invention is real
Example is applied, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
Property labour under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
A kind of method with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene of embodiment 1
The following steps are included:
Step 1 prepares phthalic anhydride
(1) catalyst 1 is prepared
By 80g Triisopropoxyvanadium(V) oxide, 10g bismuth molybdate, 200g formamide, it is configured to solution 1, with 600g isopropyl titanate, 7g oxygen
Change tin mixing and emulsifying is uniform suspension, by suspension spray on carrier alumina silicate, until the activity substance content on carrier
Reach 10%, catalyst 1 is made.
(2) catalyst 2 is prepared
By 100g ammonium metavanadate, 8g sodium molybdate, 200g formamide, it is configured to solution 2, with 600g
Isopropyl titanate, 18g tin oxide mixing and emulsifying are uniform suspension, by suspension spray on carrier alumina silicate, until
Activity substance content on carrier reaches 13%, and catalyst 2 is made.
(3) oxidation reaction
It carries out preparing phthalic anhydride in fixed bed reactors, is 30mm in internal diameter, pipe range is that the fixed bed of 3500mm is anti-
It answers in device, upper section bed loading catalyst 1, filling height is 1500mm, and lower section bed loading catalyst 2, loading height is
1000mm, both ends are sealed with quartz sand respectively, and the length of sealing two ends is 500mm；Reaction product is collected in capturing device,
For heat exchanging body, reaction heat is exported the fused salt for using forced circulation to flow outside reactor by fused salt.
In fixed bed reactors, air sample introduction flow is 5Nm3/ h, ortho-xylene concentration are 102g/Nm3, air and adjacent two
Toluene flows into reactor and is reacted, and salt temperature is 355 DEG C, and fused salt internal circulating load is 5000m3/ h, solid-bed reactor outlet,
The yield (in terms of ortho-xylene) of ortho-xylene acid anhydrides is 118%, obtains phthalic anhydride solid after cooling.
Above-mentioned phthalic anhydride can replace ortho-xylene with naphthalene, adjacent when replacing ortho-xylene to be reacted with naphthalene
The yield (in terms of naphthalene) of dimethylbenzene acid anhydrides is 118.5%.
Step 2, synthesis phthalic acid ester
(1) it feeds
Phthalic anhydride 50kg, n-butanol 25Kg, composite catalyst 0.5kg are added into reactor, at 1000r/min
Stirring 15 minutes, then heats to 95 DEG C；
The composite catalyst, in parts by weight, including following components: 5 parts of phosphotungstic acids, 1 part of tetranitro potassium platinate, 2 parts of acetyl
Acetone molybdenum.
(2) n-butanol is added dropwise
26.25kg n-butanol is added dropwise into reactor, when n-butanol is added dropwise, keeping the temperature in reactor is 105 DEG C, n-butanol
Time for adding be 30 minutes；During n-butanol is added dropwise, intermittent stirring is carried out in reactor, is stirred with the rate of 800r/min
5 minutes, stop 1 minute, as 1 period, circulation is carried out.
N-butanol total amount and the molar ratio of phthalic anhydride are 2.05:1 in step (1) and step (2).
(3) negative reaction
It is added dropwise, adjusts the pressure of reactor to 72Kpa, reaction temperature is 90 DEG C, is reacted 30 minutes.
(4) rectifying
40 DEG C are cooled to hereinafter, rectifying obtains dibutyl phthalate product, in terms of phthalic anhydride, yield to reactor
Up to 99.4%.
2 catalyst of embodiment applies test
By in the reaction product of embodiment 1, rectifying obtains dibutyl phthalate product, rectifying and dewatering；Remaining ingredient is
Catalyst (includes a small amount of unreacted complete phthalic anhydride and n-butanol), and set is used for the synthetic reaction of next group, applies 10
Secondary, the yield result of dibutyl phthalate is as follows:
The catalysis oxidation product of ortho-xylene or naphthalene of the present invention is phthalic anhydride.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of method with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene, it is characterised in that: described
Method, including prepare phthalic anhydride, synthesis phthalic acid ester；The synthesis phthalic acid ester, including feed, be added dropwise
N-butanol, negative reaction.
2. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 1
Method, it is characterised in that: phthalic anhydride, a certain amount of n-butanol, composite catalyst are added into reactor for the charging,
It is stirred, then heats to 93-97 DEG C.
3. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 1
Method, it is characterised in that: the dropwise addition n-butanol, when dropwise addition, keeping the temperature in reactor is 105 DEG C, when the dropwise addition of n-butanol
Between be 28-32 minutes.
4. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 1
Method, it is characterised in that: the negative reaction is added dropwise, and adjusts the pressure of reactor to 70-75Kpa, reaction temperature 90-
It 93 DEG C, reacts 29-33 minutes.
5. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 2
Method, it is characterised in that: the charging, the additional amount of n-butanol are the 45-50wt% of n-butanol total amount；The phthalic anhydride
With the molar ratio of n-butanol total amount are as follows: 1:2.05.
6. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 2
Method, it is characterised in that: the composite catalyst additional amount is the 0.8-1.2% of phthalic anhydride weight；The composite catalyzing
Agent, in parts by weight, including following components: 5 parts of phosphotungstic acids, 1 part of tetranitro potassium platinate, 2 parts of acetyl acetones.
7. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 1
Method, it is characterised in that: it is described to prepare phthalic anhydride, including prepare catalyst 1, prepare catalyst 2, reaction.
8. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 7
Method, it is characterised in that: the catalyst 1, active material are Triisopropoxyvanadium(V) oxide, bismuth molybdate, isopropyl titanate, tin oxide, are carried
Activity substance content on body is 9-11%, the Triisopropoxyvanadium(V) oxide, bismuth molybdate, isopropyl titanate, tin oxide mass ratio
Are as follows: 78-83:9-11:590-605:6.5-7.5.
9. a kind of side with ortho-xylene or the catalysis oxidation Product formation phthalic acid ester of naphthalene according to claim 7
Method, it is characterised in that: the catalyst 2, active material is ammonium metavanadate, sodium molybdate, isopropyl titanate, tin oxide, on carrier
Activity substance content be 12.5-13.5%；The ammonium metavanadate, sodium molybdate, isopropyl titanate, tin oxide mass ratio be 95-
105:7-9:595-610:17-19.
10. according to claim 7 a kind of with the catalysis oxidation Product formation phthalic acid ester of ortho-xylene or naphthalene
Method, it is characterised in that: the reaction, air sample introduction flow are 5Nm3/ h, ortho-xylene concentration are 102g/Nm3, reaction temperature
It is 330 DEG C.
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| CN201811056985.4A CN108997123B (en) | 2018-09-11 | 2018-09-11 | Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene |
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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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| 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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| CN104418748A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of diester phthalate by o-xylene liquid-phase oxidation and esterification coupling |
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2018
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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 |
| 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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| CN104418748A (en) * | 2013-08-22 | 2015-03-18 | 中国科学院大连化学物理研究所 | Method for preparation of diester phthalate by o-xylene liquid-phase oxidation and esterification coupling |
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