CN110357783A - A method of utilizing the power generation of p xylene oxidation residue - Google Patents
A method of utilizing the power generation of p xylene oxidation residue Download PDFInfo
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- CN110357783A CN110357783A CN201810316160.5A CN201810316160A CN110357783A CN 110357783 A CN110357783 A CN 110357783A CN 201810316160 A CN201810316160 A CN 201810316160A CN 110357783 A CN110357783 A CN 110357783A
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- ester
- mixing liquid
- steam
- power generation
- residue
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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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- 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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
- F01D15/00—Adaptations of machines or engines for special use; Combinations of engines with devices driven thereby
- F01D15/10—Adaptations for driving, or combinations with, electric generators
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/22—Methods of steam generation characterised by form of heating method using combustion under pressure substantially exceeding atmospheric pressure
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
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- Sustainable Development (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of power generation using p xylene oxidation residue, low-carbon alcohols and catalyst are added in party's normal direction oxidation residua, mixing liquid ester is obtained by catalysis dissolution esterification, most of solid residue is recycled, can reduce by 90% or more solid waste discharge.Obtained mixing liquid ester can burn for steam boiler, and the steam of generation leads to steam turbine and generates electricity.This method comprehensively utilizes paraxylene liquid phase oxidation residue, greatly reduces the discharge of solid waste, while as fuel power generation function, having very high comprehensive economy.
Description
Technical field
The present invention relates to chemical field, the side of specifically a kind of power generation using p xylene oxidation residue
Method.
Background technique
Terephthalic acid (TPA) is important large Organic Chemicals, is presently mainly obtained by p xylene oxidation.Right
Dimethylbenzene liquid phase oxidation, which prepares terephthalic acid (TPA), can generate a large amount of fragrant acids residue, and main component therein includes, to benzene
Dioctyl phthalate, phthalic acid, benzoic acid, methyl benzoic acid, p -carboxybenzaldehyde etc..And these solid residue acidity are very high, directly
The processing methods such as the landfill connect will cause serious environmental pollution, it is necessary to improve.The complicated component of these solid residues,
Change also very greatly with the various constituent contents of the fluctuation of oxidizing condition, individually recycles certain component and have little significance.And this solid is residual
Slag directly burns since acid value is high, and the reasons such as accumulation is close are insufficient so as to cause burning, and is not suitable for as fuel.If can
Aromatic acid compound in residue is obtained into the lower liquid fuel of acid value by being esterified conversion, then it can be used as power pot
The fuel of furnace is to generate electricity.This method can provide a kind of new solution for the processing of PTA residue, have apparent
Economic benefit.
Summary of the invention
In order to reduce the discharge of solid waste in paraxylene liquid phase oxidation technique, the comprehensive utilization ratio of resource is improved,
The present invention provides a kind of processing methods for paraxylene liquid phase oxidation residue.This method utilizes PTA (terephthalic acid (TPA))
Low-carbon alcohols and catalyst are added into residue using esterification for the high feature of organic acid content in residue, are dissolved by catalysis
PTA solid residue is converted the lower liquid fuel of acid value by esterification process, and the fuel as power boiler is to be sent out
Electricity.This method can provide a kind of new solution for the processing of PTA residue, have apparent economic benefit.
According to the present invention, a method of using the power generation of p xylene oxidation residue, in party's normal direction PTA oxidation residua
Low-carbon alcohols and catalyst is added, obtains mixing liquid ester by catalysis dissolution esterification, obtained mixing liquid ester can be for steaming
Boiler furnace burning, the steam of generation lead to steam turbine and generate electricity.
According to the present invention, the low-carbon alcohols are in methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol
It is one or two kinds of more than.
According to the present invention, the catalyst is hydrochloric acid, nitric acid, sulfuric acid, potassium acid sulfate, p-methyl benzenesulfonic acid, metatitanic acid alkyl
Ester, stannous oxide, one or more of aluminium oxide or acidic molecular sieve.
According to the present invention, the reactor of the catalysis dissolution esterification is closed tank reactor, and oxidation residua is added to instead
It answers in device, low-carbon alcohols, is heated with stirring to corresponding temperature, after a certain period of time, stop reaction, carry out standing and be separated by solid-liquid separation.
According to the present invention, the low-carbon alcohols quality being added is 1-40 times, preferably 2-3 times of solid residue quality；It is added
The quality for entering catalyst is the 0.5-60%, preferably 1-5% of solid residue quality.
According to the present invention, the esterification temperature be 60-250 DEG C, preferably 180-220 DEG C, pressure 0.05-
2.0MPa, preferably 1-1.5Mpa, time 1-10h, preferably 3-5h.
According to the present invention, the method also includes the processes to the thick ester product purification of mixing after esterification.The purification
Step is to divide water and rectifying, and dividing water is that stratification removes water layer, is flashed to remove the low-boiling point material in gained organic phase.
According to the present invention, resulting mixed ester is conveyed into oxygen according to the ratio that volume ratio is 1:5-1:15 and carries out burning pair
Steam boiler heating, and the steam that steam boiler generates is collected and leads to steam turbine using air supply pipe and generates electricity.
Beneficial effects of the present invention
1. PTA oxidation residua of the invention obtains mixing thick ester, undissolved solid is residual by catalysis dissolution esterification process
Slag is then used as offal treatment, it is possible to reduce the discharge of 90% or more solid residue is simply filled script discarded
Object carries out high efficiente callback and recycling, meets current green economy, environmental-friendly development topic.
2. mixing thick ester after excessive water, flash distillation, acid value is substantially reduced, and be can be used as liquid fuel and is burnt, and is led to
Processing method of the invention is crossed, the utilization rate of oxidation residua is improved, there is mixed economy type, there is apparent commercial introduction valence
Value.
Detailed description of the invention
Fig. 1 is PTA oxidation residua flow diagram.
Specific embodiment
Method provided by the invention is described in detail with reference to the accompanying drawings and examples, but does not limit this hair in any form
It is bright.
During using liquid phase oxidation production PTA (country includes ease magnificenceization, Xiamen Xiang Ludeng factory), to two
The waste residue that a kind of oxidation residua can be discharged in toluene oxidation workshop section (mainly includes terephthalic acid (TPA), M-phthalic acid, benzoic acid agent first
The mixture of yl benzoic acid), oxidation residua or paraxylene solid residue as of the present invention.
Embodiment 1
As shown in Figure 1,100g paraxylene solid residue is weighed, and 100g methanol, 98% concentrated sulfuric acid of 5g mass concentration, in height
150 DEG C of reactions carry out the process of esterification dissolution, pressure 1.5Mpa, reaction time 5h, after the process, by solid in pressure kettle
Liquid separation, liquid are to mix thick ester, and quality is 7.8g after remaining oxidized solid residue drying, can calculate oxidation residua
Removal rate is 92.2%.Gained obtains liquid through excessive water, and the product after dividing water enters flash process, by low-boiling-point substance from flash distillation 110
The extraction of DEG C tank top, resulting low-boiling-point substance is mainly unreacted low-carbon alcohols, can be recycled.Tower bottom is resulting liquid
Fuel, resulting liquid fuel and oxygen enter boiler combustion according to the volume ratio of 1:10, and measuring its combustion heat is 29 × 10^
6 joules/kilogram, final generation steam lead to steam turbine and generate electricity.
Embodiment 2-7
The reaction process of embodiment 1 is repeated, the difference is that using different solvents, catalyst and reaction condition.It is each to implement
Example specific raw material reaction condition and the results are shown in Table 1.
Table 1
This method comprehensively utilizes paraxylene liquid phase oxidation residue, greatly reduces the row of solid waste
It puts, while as fuel power generation function, there is very high comprehensive economy.
Claims (9)
1. a kind of method of the power generation using p xylene oxidation residue adds into production PTA (terephthalic acid (TPA)) oxidation residua
Enter low-carbon alcohols and catalyst, obtains mixing liquid ester by catalysis dissolution esterification, obtained mixing liquid ester can be as combustion
Expect combustion power generation.
2. according to the method for claim 1, it is characterised in that: described that fuel-fired power generation is used as to refer to obtained mixing
Liquid ester can burn as fuel for steam boiler, and the steam that steam boiler generates leads to steam turbine and generates electricity.
3. according to the method for claim 1, it is characterised in that: the low-carbon alcohols be selected from methanol, ethyl alcohol, propyl alcohol, butanol,
One of amylalcohol, hexanol, enanthol, octanol are two or more.
4. according to the method for claim 1, it is characterised in that: the catalyst is hydrochloric acid, nitric acid, sulfuric acid, hydrogen sulfate
Potassium, p-methyl benzenesulfonic acid, alkyl titanate, stannous oxide, one or more of aluminium oxide or acidic molecular sieve.
5. according to the method for claim 1, it is characterised in that: the reactor of the catalysis dissolution esterification is that closed autoclave is anti-
Device is answered, oxidation residua is added in reactor, and low-carbon alcohols and catalyst is added, is heated with stirring to corresponding temperature, certain time
Afterwards, stop reaction, carry out standing and be separated by solid-liquid separation, liquid phase is required mixing liquid ester.
6. according to method described in claim 1,3,4 or 5, it is characterised in that: the low-carbon alcohols quality being added is solid residue
1-40 times of quality, preferably 2-3 times；The quality of catalyst be added is the 0.5-60%, preferably 1- of solid residue quality
5%.
7. according to processing method described in claim 1 or 5, it is characterised in that: the esterification temperature is 60-250 DEG C, preferably
It is 180-220 DEG C, pressure 0.05-2.0MPa, preferably 1-1.5MPa, time 1-10h, preferably 3-5h.
8. processing method described in accordance with the claim 1, it is characterised in that: obtain mixing liquid ester by catalysis dissolution esterification
It afterwards, further include after being esterified to the process for mixing thick ester product purification；Then obtained mixing liquid ester can be used as fuel
It burns for steam boiler；
The step of purification is to divide water and rectifying, and dividing water is that stratification removes water layer, and rectifying is flash distillation (90-130 DEG C), is dodged
It steams to remove the low-boiling point material in gained organic phase.
9. processing method according to claim 2, it is characterised in that: obtained mixing liquid ester can be supplied as fuel
The process of steam boiler burning is that gained is obtained mixed ester and conveys oxygen according to oxygen volume ratio for the ratio of 1:10-1:15
It burns with mixed ester and steam boiler is heated, and the steam that steam boiler generates is collected and leads to vapour using air supply pipe
Turbine generates electricity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810316160.5A CN110357783A (en) | 2018-04-10 | 2018-04-10 | A method of utilizing the power generation of p xylene oxidation residue |
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| CN201810316160.5A CN110357783A (en) | 2018-04-10 | 2018-04-10 | A method of utilizing the power generation of p xylene oxidation residue |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796010A (en) * | 2004-12-29 | 2006-07-05 | 中国石化集团天津石油化工公司 | Method for synthetic using oxidation residue of para-xylene |
| JP2014070132A (en) * | 2012-09-28 | 2014-04-21 | Teijin Ltd | Process of producing polyester raw material |
| CN106187766A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of processing method of o-Xylene Oxidation in Liquid Phase residue |
| CN106187778A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of method processing o-Xylene Oxidation in Liquid Phase residue |
-
2018
- 2018-04-10 CN CN201810316160.5A patent/CN110357783A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796010A (en) * | 2004-12-29 | 2006-07-05 | 中国石化集团天津石油化工公司 | Method for synthetic using oxidation residue of para-xylene |
| JP2014070132A (en) * | 2012-09-28 | 2014-04-21 | Teijin Ltd | Process of producing polyester raw material |
| CN106187766A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of processing method of o-Xylene Oxidation in Liquid Phase residue |
| CN106187778A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院大连化学物理研究所 | A kind of method processing o-Xylene Oxidation in Liquid Phase residue |
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Application publication date: 20191022 |