CN106187778A - A kind of method processing o-Xylene Oxidation in Liquid Phase residue - Google Patents
A kind of method processing o-Xylene Oxidation in Liquid Phase residue Download PDFInfo
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- CN106187778A CN106187778A CN201510227464.0A CN201510227464A CN106187778A CN 106187778 A CN106187778 A CN 106187778A CN 201510227464 A CN201510227464 A CN 201510227464A CN 106187778 A CN106187778 A CN 106187778A
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Abstract
The invention discloses a kind of method processing o-Xylene Oxidation in Liquid Phase residue, first oxidized solid residue is liquefied by the method by the method for catalytic esterification, processes the oxidation residua after liquefaction by the technology of molecular distillation, reclaims aromatic esters from solid residue.After refined, the aromatic esters of recovery can be as solvent, and plasticizer etc. uses, and remaining high boiling component can pass through pipeline transportation to boiler room as fuel combustion.The method makes o-Xylene Oxidation in Liquid Phase residue be comprehensively utilized, and greatly reduces the discharge of solid waste, it is achieved that industrial waste residue resource.
Description
Technical field
The present invention relates to chemical field, specifically one utilizes molecular distillation technique comprehensive utilization neighbour
The method of dimethylbenzene liquid phase oxidation residue.
Background technology
Phthalate is important plasticizer, is presently mainly by o xylene oxidation product (adjacent benzene
Dioctyl phthalate, phthalic anhydride) the obtaining of esterification.O-Xylene Oxidation in Liquid Phase is anti-during preparing phthalic acid
Answering temperature high, can produce substantial amounts of fragrance acids residue, main component therein includes, phthalic acid,
P-phthalic acid, phthalic acid, benzoic acid, ar-Toluic acid, 2-carboxybenzaldehyde etc..And these are solid
The processing methods such as body residue acidity is the highest, direct landfill can cause serious environmental pollution, industrial generally
Process with burning method, although the method solves environmental problem, but waste substantial amounts of can not be again
Production-goods source, it is necessary to improve.Meanwhile, the complicated component of these solid residues, with the ripple of oxidizing condition
Dynamic various constituent contents change the most greatly, individually reclaim certain component and have little significance, and the ester of fragrance acids can
As a kind of good solvent, to obtain a kind of mixed ester kind solvent as being esterified by the fragrant acids in residue,
Can be that processing of oxidation residua provides a kind of new solution.
Molecular distillation is under vacuum, and fluid molecule is heated and escapes from liquid level, utilizes different molecular average
The method that free path difference causes surface evaporation rate different and reaches to separate.Due to during molecular distillation at Gao Zhen
Distilling under sky, required heating-up temperature is far below the boiling point under normal barometric pressure, and distillation time is short, is difficult to
Producing the components such as carbonizing matter, this process is currently and separates the distillating method that product is the gentleest.After liquefaction
Oxidized solid residue, has boiling point high, and viscosity is high, the features such as molecular weight is big, if with traditional rectification
Mode carries out reclaiming useful constituent therein, and temperature is high, it is easy to coking, forms new residue, causes blocking up
The problems such as pipe.Therefore, developing new technology becomes a critically important problem to process solid residue.Utilize
Molecular distillation reclaims useful constituent therein, and temperature is low, and efficiency is high, can avoid the problems such as coking, for
Processing of oxidized solid residue after liquefaction provides a kind of new solution.
Summary of the invention
The oxidation residua conventional process that O-phthalic acid reaction produces is prepared for about o-Xylene Oxidation in Liquid Phase
The deficiency of method, the invention provides a kind of method processing o-Xylene Oxidation in Liquid Phase residue, and the method is first
The oxidation residua of solid-state is liquefied by the method first dissolved with catalytic esterification, then processes liquefaction with molecular distillation technique
After oxidation residua, the fragrant acids component in oxidation residua is carried out esterification and separates, reclaim virtue simultaneously
Fragrant acid esters, by the method, is making up traditional method environmental pollution, while the problems such as residue utilization rate is low,
Reclaim the useful constituent in solid waste in o-Xylene Oxidation in Liquid Phase technique, improve reaction condition,
Improve the comprehensive utilization ratio of resource, reduce the discharge of solid waste.
The technical scheme is that
According to the present invention, the party's normal direction oxidation residua adds phthalic acid ester or o-toluic acid ester or
The catalyst of the mixture of the two, low-carbon alcohols and catalytic amount, dissolves consolidating after esterification is liquefied through catalysis
Body residue.Oxidation residua of the present invention stems from o-Xylene Oxidation in Liquid Phase and prepares phthalic acid process
Middle reaction temperature is high, a large amount of fragrance acids residues of generation, and main component therein includes, phthalic acid,
P-phthalic acid, phthalic acid, benzoic acid, ar-Toluic acid, 2-carboxybenzaldehyde etc..Institute of the present invention
The oxidation residua stated is solid residue.
Molecular distillation of the present invention is under vacuum, and fluid molecule is heated and escapes from liquid level, utilizes
Different molecular mean free path difference causes surface evaporation rate different and reaches the method separated, due to molecule
Distilling under a high vacuum during distillation, required heating-up temperature is far below the boiling point under normal barometric pressure, distillation
Time is short, is not likely to produce the components such as carbonizing matter, and this process is currently and separates the distillating method that product is the gentleest.
According to the present invention, phthalic acid ester includes in the esterification products of phthalic acid and C1-C8 low-carbon alcohols
One or more；O-toluic acid ester includes the esterification of o-toluic acid and C1-C8 low-carbon alcohols
One or more in product.
According to the present invention, the low-carbon alcohols added is C1-C8 alcohol, preferably methanol.
According to the present invention, described catalyst is hydrochloric acid, nitric acid, sulphuric acid, potassium acid sulfate, p-methyl benzenesulfonic acid,
One or more in alkyl titanate, Tin monoxide, aluminium oxide or molecular sieve.
The mass fraction of described hydrochloric acid is 5%-37%, and the mass fraction of described nitric acid is 5%-69%, described sulphuric acid
Mass fraction be 5-98%.
According to the present invention, the phthalic acid ester added or o-toluic acid ester or the mixture of the two it is
1-20 times of solid residue quality, preferably 2-5 times；The low-carbon alcohols quality added is solid residue quality
1-40 times, preferably 2-3 times；The quality of added catalyst is the 0.5-60% of solid residue quality,
It is preferably 1-5%.
According to the present invention, described esterification temperature is 60-250 DEG C, preferably 180-220 DEG C, and pressure is
0.05-2.0Mpa, preferably 1.0-1.5Mpa, the time is 1-10h, preferably 2-6h.
According to the present invention, it is characterised by: the operation pressure of molecular distillation is described molecular distillation technique condition:
1-100Pa, the preheating temperature of the residue after liquefaction during above-mentioned molecular distillation is 25-50 DEG C, above-mentioned molecule
During distillation, evaporator surface temperature is 50-150 DEG C.
According to the present invention, in molecular distillation technique processing procedure, mixed after first order molecular distills
Aromatic esters, obtain after multiple-grade molecular distillation be separate aromatic esters.
According to the present invention, the equipment that molecular distillation technique is used includes falling-film still, scraped film type
Molecular distillation apparatus, centrifugal molecular distillating device, modified model scraper-type molecular distillation apparatus.
Beneficial effects of the present invention
1. the oxidized solid residue after liquefaction, has boiling point high, and viscosity is high, the features such as molecular weight is big,
Compared with molecular distillation technique, traditional rectification mode carries out reclaiming the useful constituent in liquefaction rear oxidation residue,
Owing to temperature is high, it is easy to coking, form new residue, cause the problems such as plugging, utilize molecular distillation
Reclaiming useful constituent therein, temperature is low, and efficiency is high, can avoid the problems such as coking.
2. the aromatic esters that the method reclaims can be as solvent after refined, and plasticizer etc. uses.Residue
High boiling component (reboiling oil) can by pipeline transportation to boiler room as fuel combustion.The method makes
O-Xylene Oxidation in Liquid Phase residue is comprehensively utilized, and greatly reduces the discharge of solid waste, it is achieved
Industrial waste residue resource.
Detailed description of the invention
The method provided the present invention below in conjunction with embodiment is described in detail, but limits this most in any form
Bright.
Embodiment 1
Weigh 100g o xylene oxidation solid residue, add 200g dimethyl phthalate, 100g
Methanol, the concentrated sulphuric acid of 5g 98%, in autoclave, 150 DEG C of reactions carry out the process that esterification is dissolved, and pressure is
1.5Mpa, response time 5h, flash distillation removes unreacted methanol, ultimately forms high viscosity mixing liquid.
Dissolving through over-churning obtains in the feeder that liquid joins molecular distillation apparatus, and this feeder is that scraped film type divides
Sub-distilling apparatus, opens vacuum pump, and pressure reaches 30Pa, and liquid is preheating to 40 DEG C, starts blade applicator,
Opening injection valve, charging rate 1g/min, carry out molecular distillation at 80 DEG C, the light component of collection is virtue
Fragrant acid esters, restructuring is divided into high boiling oil, and obtaining mixing aromatic esters total amount is 271g, removes the adjacent benzene two added
Formic acid dimethyl ester, is 71g from the aromatic esters of Slag recovering.
Embodiment 2-7
Repeat the course of reaction of embodiment 1, except for the difference that use different solvent catalysts and reaction condition.
The concrete raw material reaction condition of each embodiment is with the results are shown in Table 1.
Table 1, embodiment 2-7
Embodiment 8
Weigh 50g o xylene oxidation solid residue, add 200g o-methyl benzoic acid methyl ester, 80g
Methanol, the concentrated sulphuric acid of 3g 98%, in autoclave, 120 DEG C of reactions carry out the process that esterification is dissolved, and pressure is
1.0Mpa, response time 5h, flash distillation removes unreacted methanol, ultimately forms high viscosity mixing liquid.
Dissolving through over-churning obtains in the feeder that liquid joins molecular distillation apparatus, and this feeder is that falling film type divides
Sub-distilling apparatus, opens vacuum pump, and pressure reaches 20Pa, and liquid is preheating to 30 DEG C, opens injection valve,
Charging rate 2g/min, carries out molecular distillation at 60 DEG C, and the light component of collection is aromatic esters, restructuring
Being divided into high boiling oil, obtaining mixing aromatic esters is 261g, removes the 200g o-methyl benzoic acid methyl ester added,
It is 61g from the aromatic esters of Slag recovering.
Embodiment 9-13
Repeat the course of reaction of embodiment 8, except for the difference that use different solvent catalysts and reaction condition.
The concrete raw material reaction condition of each embodiment is with the results are shown in Table 2.
Table 2, embodiment 9-13
Claims (10)
1. the method processing o-Xylene Oxidation in Liquid Phase residue, it is characterised in that: dissolve with catalytic esterification
Method the oxidation residua of solid-state is liquefied, then process the oxidation residua after liquefaction with molecular distillation technique, from
Oxidation residua reclaims aromatic esters.
The most in accordance with the method for claim 1, it is characterised in that: o-Xylene Oxidation in Liquid Phase residue is existed
Carrying out catalytic esterification dissolving in autoclave, flash distillation removes unreacted low-carbon alcohols, ultimately forms high viscosity mixing
Liquid, dissolves, through over-churning, the liquid that obtains and joins and carry out molecular distillation in molecular distillation equipment, collection light
Component is aromatic esters, and heavy constituent is reboiling oil.
3. according to the method described in claim 1 or 2, it is characterised in that: described catalytic esterification dissolves and is
Point to and oxidation residua adds solvent phthalic acid ester or o-toluic acid ester or the mixture of the two, then
Adding low-carbon alcohols corresponding to solvent phase and catalyst, oxidation residua, after esterification is dissolved in catalysis, is liquefied
After solid residue.
4. according to the method described in claim 1 or 2, it is characterised in that: described molecular distillation technique bar
Part: operation pressure is 1-100Pa, during molecular distillation, the preheating temperature of the residue after liquefaction is 25-50 DEG C,
During molecular distillation, evaporator surface temperature is 50-150 DEG C.
5. according to the method described in claim 1 or 2, it is characterised in that: molecular distillation technique processing procedure
In, after first order molecular distills, obtain the aromatic esters of mixing, obtain after multiple-grade molecular distillation is
The aromatic esters separated；The equipment that molecular distillation technique is used includes falling-film still, scraped film type
Molecular distillation apparatus, centrifugal molecular distillating device, modified model scraper-type molecular distillation apparatus.
The most in accordance with the method for claim 3, it is characterised in that: phthalic acid ester includes O-phthalic
Acid and one or more in the esterification products of C1-C8 low-carbon alcohols, phthalic acid ester is specially adjacent benzene
Dicarboxylic acid dimethyl ester, diethyl phthalate, dipropyl phthalate, dibutyl phthalate,
Diamyl phthalate, dihexylphthalate, dibutyl phthalate (DHP), phthalic acid two is pungent
Ester；O-toluic acid ester include the one in the esterification products of o-toluic acid and C1-C8 low-carbon alcohols or
Two or more, o-toluic acid ester is specially o-methyl benzoic acid methyl ester, o-toluic acid ethyl ester, neighbour
Ar-Toluic acid propyl ester, o-toluic acid butyl ester, o-toluic acid pentyl ester, the own ester of o-toluic acid,
O-toluic acid heptyl ester, o-toluic acid monooctyl ester, the mixture of described the two is main carbochain carbon number
Identical phthalic acid ester and the mixture of o-toluic acid ester.
The most in accordance with the method for claim 3, it is characterised in that: described low-carbon alcohols is selected from methanol, second
Alcohol, propanol, butanol, amylalcohol, hexanol, enanthol, capryl alcohol.
The most in accordance with the method for claim 3, it is characterised in that: described catalyst is mass fraction 5-37%
Hydrochloric acid, the nitric acid of mass fraction 5-69%, the sulphuric acid of mass fraction 5%-98%, potassium acid sulfate, to toluene
One or more in sulfonic acid, alkyl titanate, Tin monoxide, aluminium oxide or molecular sieve, wherein,
Alkyl titanate is butyl titanate, tetraethyl titanate, the one in tetraisopropyl titanate.
The most in accordance with the method for claim 3, it is characterised in that: the phthalic acid ester that added and/or
The gross mass of o-toluic acid ester is 1-20 times of solid residue quality, preferably 2-5 times；Added
Low-carbon alcohols quality is 1-40 times of solid residue quality, preferably 2-3 times；The quality of added catalyst is
The 0.5-60% of solid residue quality, preferably 5-10%.
The most in accordance with the method for claim 3, it is characterised in that: described esterification temperature is 60-250 DEG C,
Being preferably 180-220 DEG C, pressure is 0.05-2.0Mpa, preferably 1.0-1.5Mpa, and the time is 1-10h,
It is preferably 2-6h.
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| CN201510227464.0A CN106187778B (en) | 2015-05-06 | 2015-05-06 | A method of processing o-Xylene Oxidation in Liquid Phase residue |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357783A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院大连化学物理研究所 | A method of utilizing the power generation of p xylene oxidation residue |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1490300A (en) * | 2002-10-15 | 2004-04-21 | 上海帮侬生物技术有限公司 | Industrial method for producing benzene carboxylic acid ester from dreg of coarse products of p-phthalic acid |
| CN1611482A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid oxidation residue recovery and utilization method |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| CN102516080A (en) * | 2011-09-30 | 2012-06-27 | 白英 | Recovery process of PX oxidation residues and recovery system device thereof |
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2015
- 2015-05-06 CN CN201510227464.0A patent/CN106187778B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490300A (en) * | 2002-10-15 | 2004-04-21 | 上海帮侬生物技术有限公司 | Industrial method for producing benzene carboxylic acid ester from dreg of coarse products of p-phthalic acid |
| CN1611482A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid oxidation residue recovery and utilization method |
| CN1611481A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Terephthalic acid and water scrubbing residue recovery and utilization method |
| CN102516080A (en) * | 2011-09-30 | 2012-06-27 | 白英 | Recovery process of PX oxidation residues and recovery system device thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357783A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院大连化学物理研究所 | A method of utilizing the power generation of p xylene oxidation residue |
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