CN102516080A - Recovery process of PX oxidation residues and recovery system device thereof - Google Patents
Recovery process of PX oxidation residues and recovery system device thereof Download PDFInfo
- Publication number
- CN102516080A CN102516080A CN2011103191473A CN201110319147A CN102516080A CN 102516080 A CN102516080 A CN 102516080A CN 2011103191473 A CN2011103191473 A CN 2011103191473A CN 201110319147 A CN201110319147 A CN 201110319147A CN 102516080 A CN102516080 A CN 102516080A
- Authority
- CN
- China
- Prior art keywords
- rectifying tower
- residue
- esterification
- tail gas
- reclaims
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a recovery process of PX (p-xylene) oxidation residues, and the process comprises primary treatment, secondary esterification, fine distillation, ion exchange, and subsequent treatment of wastewater, exhaust gas and waste residues. The invention also discloses a recovery system device used for the recovery process of PX oxidation residues. The device consists of a high temperature flash dryer, a pulverizer, a reaction dissolving kettle, a first esterification instrument, a second esterification instrument, series of rectification towers, an ion exchange instrument, a wastewater treatment instrument and a tail gas absorption tower that are connected in order, and also includes a methanol recovery system. The process of the invention can extract various material components in large amounts and high purity, has low requirement for production equipment and basically no corrosion, and realizes recycling of wastes, which can achieve resource utilization to the utmost and a highest utilization rate. Meanwhile, the process in the invention solves the environmental protection pressure of enterprises, basically realizes no three wastes, thus being consistent with the green environmental protection concept of low carbon and having competitive edges.
Description
Technical field
The present invention relates to a kind of recovery technology of PX oxidation residua, also relate to a kind of recovering system of recovery technology of the PX of being used for oxidation residua.
Background technology
Since the reform and opening-up, the China's oil chemical engineering industry is developed on an unprecedented scale, and p-Xylol nearly all is used to produce PTA; In process of production; There is a large amount of side reactions to take place, and also has residue to produce, be i.e. the PX oxidation residua; Component is complicated, contains a large amount of phenylformic acid, terephthalic acid, m-phthalic acid, p-methylbenzoic acid, cobalt, manganese and other organic compositions; Because complicated component and composition are fixing, and its cost recovery is handled high, people generally adopt following method:
One, be directly residue to be buried, though simple, environment is caused very big and immeasurable risk, the environment around the severe contamination;
Two, be direct burning, this can produce a large amount of carbonic acid gas, will aggravate Greenhouse effect, does not meet the requirement of national current low-carbon environment-friendly;
Three, add alkaline purification, generate a large amount of mud, also be to adopt to bury processing, can cause environmental pollution equally, do not meet the National Environmental requirement;
In residue, these compositions all are of great use, if do not reclaim, will cause the wasting of resources; If can reclaim, not only useful composition can be extracted, and these residues can be handled, kill two birds with one stone!
, existing numerous light textile enterprises and printing and dyeing mill are raw material with PTA, produce many PTA residue pollutents for this reason; The CDO value that contains simultaneously increases, and the influence discharging not only causes great pressure to environmental protection; Cause heavy burden to enterprise, also seriously restrict the development of industry; The directly discharging if do not handle, this obviously is worthless.A lot of process quilt exploitations is arranged for this reason, handle oxidation residua, but there is certain deficiency in existing technology:
1, extraction useful matter component is few, only extracts phenylformic acid in the general technology, and component does not generally extract in addition, causes the wasting of resources;
2, extract acid, generally all can requirement be arranged to equipment, and corrosive nature is arranged, this can increase production cost, and also environmental protection early causes certain pressure simultaneously;
3, in some technologies, the esterification efficient of acid is not high, in recrystallization, also need add methyl esters for this reason and carry out repeatedly esterification, to improve esterification yield; Carry out recrystallization, can cause equipment to stop up, influence the raising of production efficiency;
4, because esterification efficient is not high; All there is certain influence in also not esterified terephthalic acid, m-phthalic acid and the phenylformic acid of producing for equipment, environment and staff; It or not long-term plan for this reason; Do not meet low-carbon (LC), environmental protection and green notion that country is advocated, and Scientific Outlook on Development thought;
5, products obtained therefrom is a mixed ester, if for this reason at the follow-up needs of composition separately, also need further to separate; This can increase technology; And then the configuration, the artificial that relate to production unit dispose and the demand in place, cause production cost to increase, and are unfavorable for enterprise's persistent competition on market;
6, since the composition in the oxidation residua not fully or major part be not extracted, cause extracting the back residual material, also can continue influence and contaminate environment, be unfavorable for long-run development;
7, in order to obtain highly purified product, the process of existing manufacturing technique is complicated;
8, waste gas, waste residue and the waste water of the generation in the existing technology well do not obtain handling, and cause influencing the environment of periphery, the restriction enterprise development.
This shows that addressing the above problem is extremely urgent.
In view of this, the inventor has done deep research to this, by feat of the experience of being engaged in relevant industries for many years and practice; Design a kind of recovery technology of PX oxidation residua, it is many and purity is high that this technology can be extracted various material compositions, and esterification yield is high in whole process of production; Require low and do not have corrosion basically for production unit; Realize regenerated resource development and utilization, and make its refuse maximum resourceization and the highest utilization ratio, have competitive edge; The inventor designs the recovering system that a kind of PX of being used for oxidation residua reclaims technology, and this system and device structure design is ingenious and satisfy environmental protection, green and low-carbon (LC) requirement, no three wastes generation when being used for production technique basically; Be that waste residue reuses always; Reach the highest rate of utilization, waste gas focuses on, and makes no waste gas produce; Waste water is treated promptly reusable, and this case produces thus.
Summary of the invention
One of the object of the invention, it is many and purity is high to be to provide a kind of recovery technology of PX oxidation residua, this technology can extract various material compositions; Esterification yield is high in whole process of production, requires low and does not have corrosion basically, the realization regenerated resource development and utilization for production unit; And make its refuse maximum resourceization and the highest utilization ratio, solve environmental protection of enterprise pressure simultaneously, the no three wastes of basic realization; Make Sustainable Development of Enterprises to meet low-carbon (LC) environmental protection notion, have competitive edge.
To achieve these goals, technical scheme of the present invention is following:
A kind of recovery technology of PX oxidation residua is characterized in that may further comprise the steps:
The first step, the PX oxidation residua is carried out rough handling:
(1), be 2%-7% with the contained moisture of PX oxidation residua high temperature expansion drying to residue;
(2), pulverization process, the residue after pulverization process is less than 15 orders;
(3), be made into slurry, stir, put into reaction dissolution kettle heating and constant temperature 5-10 minute, filtered while hot directly is cooled to crystallization, obtains nitration mixture residue and filtration residue after the filtration with water;
In second step, the nitration mixture residue is recycled:
(1), carry out the secondary esterification:
Esterification for the first time: in the nitration mixture residue; Adding is according to mol ratio 1: 7-1: 10 methyl alcohol and according to the ferric sulfate of total mass ratio 5 ‰-7 ‰; This moment, temperature of reaction was: 120 ℃-180 ℃, the reaction times is 4-6h, reclaims methyl alcohol through methanol distillation column;
Esterification for the second time: continue to add and 1: 5-1: 8 methyl alcohol, proceed reaction, carry out the closed spinning behind the reaction terminating, reclaim methyl alcohol through methanol distillation column;
(2), then feeding serial rectifying tower successively according to order carries out rectification process:
In first rectifying tower, it is 199.5 ℃ that temperature is set, and reclaims cooling and obtains oil of Niobe; Reflux ratio is: 0-5; Stage number: 20-40;
In second rectifying tower, it is 222.5 ℃ that temperature is set, and reclaims to obtain methyl p-methyl benzoate; Reflux ratio is: 0-5; Stage number: 30-70;
In the 3rd rectifying tower, it is 243.5 ℃ that temperature is set, and reclaims cooling and obtains tetrabromoethane; Reflux ratio is: 0-5; Stage number: 10-50;
In the 4th rectifying tower, it is 282 ℃ that temperature is set, and reclaims cooling and obtains dimethyl isophthalate; Reflux ratio is: 0-7; Stage number: 20-80;
In the 5th rectifying tower, it is 288 ℃ that temperature is set, and reclaims cooling and obtains DMT. Dimethyl p-benzenedicarboxylate; Reflux ratio is: 0-7; Stage number: 10-80;
In the 3rd step, last residue in second step mixes with filtration residue in the first step, handles, and may further comprise the steps:
(1), mixed residue is mixed with water, acetic acid, through making beating evenly and filter and obtain the aqueous solution;
(2), carry out ion exchange treatment, extract cobalt and manganese with strongly acidic cationic exchange resin;
(3), last residue is restored in the first step with new PX oxidation residua continues to participate in treatment scheme;
The 4th step got into tail gas absorber centralized collection tail gas, went on foot (1) and second through supercharging, the condensing and recycling the first step, second and went on foot the tail gas that each rectifying tower is discharged in the serial rectifying tower in (2);
In the 5th step, with resulting waste water in above each step (comprising washing water, sewage and other waste water), focus in the entering wastewater treatment equipment, to recycle water resources.
Further, the recovery methyl alcohol in said second step (1), its step comprises:
(1), concentrate distillation, remove redundant moisture, obtain the higher methanol solution of concentration;
(2), rectification process;
(3), condensing and recycling, obtain the methyl alcohol of high density.
Two of the object of the invention, the recovering system that is to provide a kind of PX of being used for oxidation residua to reclaim technology, this system and device structure design is ingenious and satisfy environmental protection, green and low-carbon (LC) requirement when being used for production technique basically; The no three wastes produce; Be that waste residue reuses always, reach the highest rate of utilization, waste gas focuses on; Make no waste gas produce, waste water is treated promptly reusable.
To achieve these goals, technical scheme of the present invention is following:
A kind of recovering system that is used for PX oxidation residua recovery technology; It is characterized in that: comprise connecting high temperature expansion drying device, kibbler, reaction dissolution kettle, the first esterification device, the second esterification device, serial rectifying tower, ion exchange unit, wastewater treatment equipment and the tail gas absorber that is provided with successively; Also comprise methanol recovery system; This methanol recovery system comprises a plurality of methanol distillation columns, and the said first esterification device and the second esterification device are connected with independently methanol distillation column respectively separately; Said serial rectifying tower comprises first rectifying tower, second rectifying tower, the 3rd rectifying tower, the 4th rectifying tower and the 5th rectifying tower; Said tail gas absorber and high temperature expansion drying device, kibbler, methanol recovery system, and be connected to be provided with and carry out tail gas and absorb with each rectifying tower in the serial rectifying tower; Said wastewater treatment equipment and high temperature expansion drying device, reaction dissolution kettle, methanol recovery system, ion exchange unit, tail gas absorber, and is connected setting with each rectifying tower in the serial rectifying tower, to recycle gained waste water.
Further, said methanol distillation column comprises head tank, tundish and absorption tower, and said tundish are provided with the spark arrester of band vacuum pressure valves.
The setting of methanol distillation column makes production cost reduce greatly, and the methyl alcohol after reclaiming can continue to return use; In the Methanol Recovery process, spark arrester has been installed, improved the SF of equipment and total system, because methyl alcohol is volatile, not only human body there is injury, and also inflammable and explosive, if suitably do not handle, potentially dangerous is well imagined.
Further, said wastewater treatment equipment comprises accident pool, equalizing tank, anaerobic pond, intermediate pool, aeration tank, Aerobic Pond, settling tank, in-depth treating pond, film treating pond and the ozonize pond that connects setting successively.
The setting of wastewater treatment equipment, major function are to handle waste water, comprise trade effluent that each production link and processing, washing obtain or the like; Through wastewater treatment equipment, mainly be the organism that carries out some difficult degradations of acidification degraded in the anaerobic pond, pass through Aerobic Pond again; Let active sludge carry out aerobic repiration, further resolve into inorganics to organism, handle through simple process again; Handle and ozone sterilization like film, promptly in process of production reusable, environment is had no effect.
Further, said tail gas absorber comprises inlet pipe, outlet pipe and absorption processing enter, and this absorption processing enter comprises water tourie, organic solvent tourie and the alkaline solution tourie that connects setting successively.
The setting of tail gas absorber, major function are in order to realize non-exhaust emission, environment to be had no effect.The water tourie that sets gradually, organic solvent are inhaled tourie and alkali tourie, utilize the characteristic of dissolving each other, other organic substances such as the water that contains in the absorbing waste gas, methyl alcohol.
A beneficial effect of the present invention:,, unfortunately tangible if do not recycle because content is abundant in the PX oxidation residua! In the PX oxidation residua; Contain phenylformic acid, to methyl benzoic acid, bromine, m-phthalic acid and terephthalic acid, cobalt, compositions such as manganese; Because the recovery complex process of acids; And have corrosion for some equipment, the time one can influence the performance of equipment for a long time, increases equipment cost and the workload of maintaining or maintaining; This technology can extract that various material compositions are many and purity is high, and esterification yield is high in whole process of production, requires low and does not have corrosion basically for production unit; Realize regenerated resource development and utilization, and make its refuse maximum resourceization and the highest utilization ratio, solve environmental protection of enterprise pressure simultaneously; The no three wastes of basic realization; Make Sustainable Development of Enterprises to meet low-carbon (LC) environmental protection notion, have competitive edge.
Wherein, catalyzer adopts ferric sulfate, can realize catalytic efficiency (efficiently, improves esterification yield, reduces process complexity, enhances productivity; Demand for methyl alcohol just greatly reduces, and relevant devices and environmental requirement also reduced, and improves the market competitiveness of enterprises.
Adopting and carry out rectification process in the serial rectifying tower, is the boiling point that utilizes different substances, comes independent extraction separation material, and not only purity is high, and efficient height and technology are simple.
In the whole process of production, owing to the most of useful matter in the oxidation residua is extracted, and last residue is returned and new oxidation residua continuation extraction; So have no waste residue to produce; Environment is not had pressure, and the environment around can not influencing meets the green requirement of national low-carbon environment-friendly.
By on can know, the present invention, it is many and purity is high that this technology can be extracted various material compositions; Esterification yield is high in whole process of production, requires low and does not have corrosion basically, the realization regenerated resource development and utilization for production unit; And make its refuse maximum resourceization and the highest utilization ratio, have competitive edge.
This system and device structure design is ingenious and satisfy environmental protection, green and low-carbon (LC) requirement when being used for production technique basically, and the no three wastes produce, and promptly waste residue reuses always; Reach the highest rate of utilization; Waste gas focuses on, and makes no waste gas produce, and waste water is treated promptly reusable.
In order further to explain technical scheme of the present invention, come the present invention is set forth in detail through specific embodiment below.
Description of drawings
Fig. 1 is the structural representation of the recovering system of the recovery technology that is used for the PX oxidation residua among the present invention;
Fig. 2 is methanol distillation column structural representation among the present invention;
Fig. 3 is the structural representation of wastewater treatment equipment among the present invention;
Fig. 4 is the structural representation of tail gas absorber among the present invention.
High temperature expansion drying device 1 kibbler 2
Reaction dissolution kettle 3 first esterification devices 4
The second esterification device, 5 serial rectifying tower 6
Water tourie 903 organic solvent touries 904
Embodiment
The present invention relates to a kind of recovery technology of PX oxidation residua, it is characterized in that may further comprise the steps:
The first step, the PX oxidation residua is carried out rough handling:
(1), the PX oxidation residua being put into high temperature expansion drying device 1, to carry out the contained moisture of high temperature expansion drying to residue be 2%-7%;
(2), in kibbler 2 pulverization process, the residue after pulverization process is less than 15 orders;
(3), be made into slurry, stir, put into the heating of reaction dissolution kettle 3 and constant temperature 5-10 minute, filtered while hot directly is cooled to crystallization, obtains nitration mixture residue and filtration residue after the filtration with water;
In this step, carry out the high temperature expansion drying, removed most of moisture content, be beneficial to pulverizing.After pulverizing through kibbler, be beneficial to the dissolution rate and the esterification yield of participating in reaction in following each step, improving various materials, also just improved the extraction yield of material.Relatively, pulverize more for a short time, speed of response could be faster, and efficient is higher, and the amount of extracting substance is how!
In second step, the nitration mixture residue is recycled:
(1), carry out the secondary esterification:
Esterification for the first time: in the nitration mixture residue; Adding is according to mol ratio 1: 7-1: 10 methyl alcohol and according to the ferric sulfate of total mass ratio 5 ‰-7 ‰; This moment, temperature of reaction was: 120 ℃-180 ℃, the reaction times is 4-6h, reclaims methyl alcohol through methanol distillation column 11;
Esterification for the second time: continue to add and 1: 5-1: 8 methyl alcohol, proceed reaction, carry out the closed spinning behind the reaction terminating, reclaim methyl alcohol through methanol distillation column 11;
In the secondary esterification, wherein, catalyzer adopts ferric sulfate, can realize catalytic efficiency (efficiently, improves esterification yield, reduces process complexity, enhances productivity; Demand for methyl alcohol just greatly reduces, and relevant devices and environmental requirement also reduced, and improves the market competitiveness of enterprises.Carrying out the secondary esterification, is for higher esterification yield, and height is more than 99%! Esterification yield one height, the rectification process in the next step just can be brought the high recovery.
(2), then feeding serial rectifying tower 6 successively according to order carries out rectification process:
In first rectifying tower, it is 199.5 ℃ that temperature is set, and reclaims cooling and obtains oil of Niobe; Reflux ratio is: 0-5; Stage number: 20-40;
In second rectifying tower, it is 222.5 ℃ that temperature is set, and reclaims to obtain methyl p-methyl benzoate; Reflux ratio is: 0-5; Stage number: 30-70;
In the 3rd rectifying tower, it is 243.5 ℃ that temperature is set, and reclaims cooling and obtains tetrabromoethane; Reflux ratio is: 0-5; Stage number: 10-50;
In the 4th rectifying tower, it is 282 ℃ that temperature is set, and reclaims cooling and obtains dimethyl isophthalate; Reflux ratio is: 0-7; Stage number: 20-80;
In the 5th rectifying tower, it is 288 ℃ that temperature is set, and reclaims cooling and obtains DMT. Dimethyl p-benzenedicarboxylate; Reflux ratio is: 0-7; Stage number: 10-80;
Adopting in the serial rectifying tower 6 and carry out rectification process, is the boiling point that utilizes different substances, comes independent extraction separation material, and not only purity is high, and efficient height and technology are simple, also increases substantially for the working efficiency of whole technology.
In the 3rd step, last residue in second step mixes with filtration residue in the first step, handles, and may further comprise the steps:
(1), mixed residue is mixed with water, acetic acid, through making beating evenly and filter and obtain the aqueous solution;
(2), carry out ion exchange treatment, extract cobalt and manganese with strongly acidic cationic exchange resin;
(3), last residue is restored in the first step with new PX oxidation residua continues to participate in treatment scheme;
The 4th step got into tail gas absorber 9 centralized collection tail gas, went on foot (1) and second through supercharging, the condensing and recycling the first step, second and went on foot the tail gas that each rectifying tower is discharged in the serial rectifying tower 6 in (2);
In this step, handle waste gas and make exhaust gas emission up to standard, the environment around not influencing meets Sustainable development! This tail gas absorber all collects the waste gas in each step and focuses on, and raises the efficiency.
In the 5th step, with resulting waste water in above each step (comprising washing water, sewage and other waste water), focus in the entering wastewater treatment equipment 8, to recycle water resources.
This step main processing waste water, not only the conserve water resource has also reduced production cost, and to also not influencing with environment, meets the green requirement of national environmental protection.
Further, the recovery methyl alcohol in said second step (1), its step comprises:
(1), concentrate distillation, remove redundant moisture, obtain the higher methanol solution of concentration;
(2), rectification process;
(3), condensing and recycling, obtain the methyl alcohol of high density.
Fig. 1 is to shown in Figure 4; The invention still further relates to a kind of recovering system of the PX of being used for oxidation residua recovery technology; It is characterized in that: comprise successively connecting the high temperature expansion drying device 1 that is provided with, kibbler 2, reaction dissolution kettle 3, the first esterification device 4, the second esterification device 5, serial rectifying tower 6, ion exchange unit 7, wastewater treatment equipment 8 and tail gas absorber 9; Also comprise methanol recovery system 10; This methanol recovery system 10 comprises a plurality of methanol distillation columns 11, and the said first esterification device 5 and the second esterification device 6 are connected with independently methanol distillation column 11 respectively separately; Said serial rectifying tower 6 comprises first rectifying tower, second rectifying tower, the 3rd rectifying tower, the 4th rectifying tower and the 5th rectifying tower; Said tail gas absorber 9 and high temperature expansion drying device 1, kibbler 2, methanol recovery system 10, and is connected to be provided with and carries out the tail gas absorption with each rectifying tower in the serial rectifying tower 6; Said wastewater treatment equipment 8 and high temperature expansion drying device 1, reaction dissolution kettle 3, methanol recovery system 10, ion exchange unit 7, tail gas absorber 9, and is connected setting with each rectifying tower in the serial rectifying tower 6, to recycle gained waste water.
Further be provided with, said methanol distillation column 11 comprises head tank 101, tundish 102 and absorption tower 103, and said tundish 102 are provided with the spark arrester 104 of band vacuum pressure valves.
The setting of methanol distillation column 11 makes production cost reduce greatly, and the methyl alcohol after reclaiming can continue to return use; In the Methanol Recovery process, spark arrester 104 has been installed, improved the SF of equipment and total system, because methyl alcohol is volatile, not only human body there is injury, and also inflammable and explosive, if suitably do not handle, potentially dangerous is well imagined.
Further be provided with, said wastewater treatment equipment 8 comprises accident pool 801, equalizing tank 802, anaerobic pond 803, intermediate pool 804, aeration tank 805, Aerobic Pond 806, settling tank 807, in-depth treating pond 808, film treating pond 809 and the ozonize pond 810 that connects setting successively.
The setting of wastewater treatment equipment 8, major function are to handle waste water, comprise trade effluent that each production link and processing, washing obtain or the like; Through wastewater treatment equipment, mainly be the organism that carries out some difficult degradations of acidification degraded in the anaerobic pond 803, again through Aerobic Pond 806; Let active sludge carry out aerobic repiration; Further resolve into inorganics to organism, handle through simple process again, handle and ozone sterilization like film; Be in process of production reusable, environment is had no effect.
Further be provided with, said tail gas absorber 9 comprises inlet pipe 901, outlet pipe 902 and absorbs processing enter that this absorption processing enter comprises water tourie 903, organic solvent tourie 904 and the alkaline solution tourie 905 that connects setting successively.
The setting of tail gas absorber 9, major function are in order to realize non-exhaust emission, environment to be had no effect.The water tourie 903 that sets gradually, organic solvent are inhaled tourie 904 and alkali tourie 905, utilize the characteristic of dissolving each other, other organic substances such as the water that contains in the absorbing waste gas, methyl alcohol.
By on can know that it is many and purity is high that this technology can be extracted various material compositions, esterification yield is high in whole process of production; Require low and do not have corrosion basically for production unit, realize regenerated resource development and utilization, and make its refuse maximum resourceization and the highest utilization ratio; Solve environmental protection of enterprise pressure simultaneously, basic realize the no three wastes, make Sustainable Development of Enterprises; Meet low-carbon (LC) environmental protection notion, have competitive edge.
In the whole process of production, owing to the most of useful matter in the oxidation residua is extracted, and last residue is returned and new oxidation residua continuation extraction; So have no waste residue to produce; Environment is not had pressure, and the environment around can not influencing meets the green requirement of national low-carbon environment-friendly.
Should the system and device structure design ingenious and satisfy environmental protection, green and low-carbon (LC) requirement basically when being used for production technique, the no three wastes produce, and promptly waste residue reuses always; Reach the highest rate of utilization; Waste gas focuses on, and makes no waste gas produce, and waste water is treated promptly reusable.
Embodiment 1
A kind of recovery technology of PX oxidation residua is characterized in that may further comprise the steps:
The first step, the PX oxidation residua is carried out rough handling:
(1), be 2% with the contained moisture of PX oxidation residua high temperature expansion drying to residue;
(2), pulverization process, the residue after pulverization process is 10 orders;
(3), be made into slurry, stir, put into dissolution kettle heating and constant temperature 5 minutes, filtered while hot directly is cooled to crystallization, obtains nitration mixture residue and filtration residue after the filtration with water;
In second step, the nitration mixture residue is recycled:
(1), carry out the secondary esterification:
Esterification for the first time: in the nitration mixture residue, add according to 1: 7 methyl alcohol of mol ratio with according to the ferric sulfate of total mass ratio 5 ‰, this moment, temperature of reaction was: 130 ℃, the reaction times is 4h, reclaims methyl alcohol through methanol distillation column 11;
Esterification for the second time: continue to add and 1: 5 methyl alcohol, proceed reaction, carry out the closed spinning behind the reaction terminating, reclaim methyl alcohol through methanol distillation column 11;
(2), then feeding serial rectifying tower 6 successively according to order carries out rectification process:
In first rectifying tower, it is 199.5 ℃ that temperature is set, and reclaims cooling and obtains oil of Niobe; Reflux ratio is: 0; Stage number: 40;
In second rectifying tower, it is 222.5 ℃ that temperature is set, and reclaims to obtain methyl p-methyl benzoate; Reflux ratio is: 5; Stage number: 35;
In the 3rd rectifying tower, it is 243.5 ℃ that temperature is set, and reclaims cooling and obtains tetrabromoethane; Reflux ratio is: 4; Stage number: 30;
In the 4th rectifying tower, it is 282 ℃ that temperature is set, and reclaims cooling and obtains dimethyl isophthalate; Reflux ratio is: 4; Stage number: 80;
In the 5th rectifying tower, it is 288 ℃ that temperature is set, and reclaims cooling and obtains DMT. Dimethyl p-benzenedicarboxylate; Reflux ratio is: 7; Stage number: 60;
In the 3rd step, last residue in second step mixes with filtration residue in the first step, handles, and may further comprise the steps:
(1), mixed residue is mixed with water, acetic acid, through making beating evenly and filter and obtain the aqueous solution;
(2), carry out ion exchange treatment, extract cobalt and manganese with strongly acidic cationic exchange resin;
(3), last residue is restored in the first step with new PX oxidation residua continues to participate in treatment scheme;
The 4th step got into tail gas absorber 9 centralized collection tail gas, went on foot (1) and second through supercharging, the condensing and recycling the first step, second and went on foot the tail gas that each rectifying tower is discharged in the serial rectifying tower 6 in (2);
In the 5th step, with resulting waste water in above each step (comprising washing water, sewage and other waste water), focus in the entering wastewater treatment equipment 8, to recycle water resources.
Wherein, the recovery methyl alcohol in said second step (1), its step comprises:
(1), concentrate distillation, remove redundant moisture, obtain the higher methanol solution of concentration;
(2), rectification process;
(3), condensing and recycling, obtain the methyl alcohol of high density.
The process of present embodiment 2-5 is identical with embodiment 1, and the parameter and the result of recycling process see table 1:
The above is merely embodiments of the invention, is not the restriction to this case design, and all equivalent variations of doing according to the design key of this case all fall into the protection domain of this case.
Claims (6)
1. the recovery technology of a PX oxidation residua is characterized in that may further comprise the steps:
The first step, the PX oxidation residua is carried out rough handling:
(1), be 2%-7% with the contained moisture of PX oxidation residua high temperature expansion drying to residue;
(2), pulverization process, the residue after pulverization process is less than 15 orders;
(3), be made into slurry, stir, put into reaction dissolution kettle heating and constant temperature 5-10 minute, filtered while hot directly is cooled to crystallization, obtains nitration mixture residue and filtration residue after the filtration with water;
In second step, the nitration mixture residue is recycled:
(1), carry out the secondary esterification:
Esterification for the first time: in the nitration mixture residue; Adding is according to mol ratio 1: 7-1: 10 methyl alcohol and according to the ferric sulfate of total mass ratio 5 ‰-7 ‰; This moment, temperature of reaction was: 120 ℃-180 ℃, the reaction times is 4-6h, reclaims methyl alcohol through methanol distillation column;
Esterification for the second time: continue to add and 1: 5-1: 8 methyl alcohol, proceed reaction, carry out the closed spinning behind the reaction terminating, reclaim methyl alcohol through methanol distillation column;
(2), then feeding serial rectifying tower successively according to order carries out rectification process:
In first rectifying tower, it is 199.5 ℃ that temperature is set, and reclaims cooling and obtains oil of Niobe; Reflux ratio is: 0-5; Stage number: 20-40;
In second rectifying tower, it is 222.5 ℃ that temperature is set, and reclaims to obtain methyl p-methyl benzoate; Reflux ratio is: 0-5; Stage number: 30-70;
In the 3rd rectifying tower, it is 243.5 ℃ that temperature is set, and reclaims cooling and obtains tetrabromoethane; Reflux ratio is: 0-5; Stage number: 10-50;
In the 4th rectifying tower, it is 282 ℃ that temperature is set, and reclaims cooling and obtains dimethyl isophthalate; Reflux ratio is: 0-7; Stage number: 20-80;
In the 5th rectifying tower, it is 288 ℃ that temperature is set, and reclaims cooling and obtains DMT. Dimethyl p-benzenedicarboxylate; Reflux ratio is: 0-7; Stage number: 10-80;
In the 3rd step, last residue in second step mixes with filtration residue in the first step, handles, and may further comprise the steps:
(1), mixed residue is mixed with water, acetic acid, through making beating evenly and filter and obtain the aqueous solution;
(2), carry out ion exchange treatment, extract cobalt and manganese with strongly acidic cationic exchange resin;
(3), last residue is restored in the first step with new PX oxidation residua continues to participate in treatment scheme;
The 4th step got into tail gas absorber centralized collection tail gas, went on foot (1) and second through supercharging, the condensing and recycling the first step, second and went on foot the tail gas that each rectifying tower is discharged in the serial rectifying tower in (2);
In the 5th step, with resulting waste water in above each step (comprising washing water, sewage and other waste water), focus in the entering wastewater treatment equipment, to recycle water resources.
2. reclaim technology according to the said a kind of PX oxidation residua of claim 1, it is characterized in that: the recovery methyl alcohol in said second step (1), its step comprises:
(1), concentrate distillation, remove redundant moisture, obtain the higher methanol solution of concentration;
(2), rectification process;
(3), condensing and recycling, obtain the methyl alcohol of high density.
3. one kind is used for the recovering system that the said PX oxidation residua of claim 1 reclaims technology; It is characterized in that: comprise connecting high temperature expansion drying device, kibbler, reaction dissolution kettle, the first esterification device, the second esterification device, serial rectifying tower, ion exchange unit, wastewater treatment equipment and the tail gas absorber that is provided with successively; Also comprise methanol recovery system; This methanol recovery system comprises a plurality of methanol distillation columns, and the said first esterification device and the second esterification device are connected with independently methanol distillation column respectively separately; Said serial rectifying tower comprises first rectifying tower, second rectifying tower, the 3rd rectifying tower, the 4th rectifying tower and the 5th rectifying tower; Said tail gas absorber and high temperature expansion drying device, kibbler, methanol recovery system, and be connected to be provided with and carry out tail gas and absorb with each rectifying tower in the serial rectifying tower; Said wastewater treatment equipment and high temperature expansion drying device, reaction dissolution kettle, methanol recovery system, ion exchange unit, tail gas absorber, and is connected setting with each rectifying tower in the serial rectifying tower, to recycle gained waste water.
4. according to the said a kind of recovering system that the PX oxidation residua reclaims technology that is used for of claim 3, it is characterized in that: said methanol distillation column, comprise head tank, tundish and absorption tower, said tundish are provided with the spark arrester of band vacuum pressure valves.
5. according to the said a kind of recovering system that the PX oxidation residua reclaims technology that is used for of claim 3, it is characterized in that: said wastewater treatment equipment comprises accident pool, equalizing tank, anaerobic pond, intermediate pool, aeration tank, Aerobic Pond, settling tank, in-depth treating pond, film treating pond and the ozonize pond that connects setting successively.
6. according to the said a kind of recovering system that the PX oxidation residua reclaims technology that is used for of claim 3; It is characterized in that: said tail gas absorber comprises inlet pipe, outlet pipe and absorption processing enter, and this absorption processing enter comprises water tourie, organic solvent tourie and the alkaline solution tourie that connects setting successively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103191473A CN102516080A (en) | 2011-09-30 | 2011-09-30 | Recovery process of PX oxidation residues and recovery system device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103191473A CN102516080A (en) | 2011-09-30 | 2011-09-30 | Recovery process of PX oxidation residues and recovery system device thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102516080A true CN102516080A (en) | 2012-06-27 |
Family
ID=46287221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103191473A Pending CN102516080A (en) | 2011-09-30 | 2011-09-30 | Recovery process of PX oxidation residues and recovery system device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516080A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112968A (en) * | 2013-03-01 | 2013-05-22 | 山东潍坊润丰化工有限公司 | Method for treating high-COD (Chemical Oxygen Demand) components in phenoxyalkanoic acid production wastewater |
| CN105017022A (en) * | 2015-07-20 | 2015-11-04 | 浙江大学 | Method for methyl esterification recovery and recycle of PTA oxidation residue |
| CN105102418A (en) * | 2014-02-07 | 2015-11-25 | Lg化学株式会社 | Plasticizers, resin composition, and method for manufacturing plasticizers and resin composition |
| CN105111074A (en) * | 2015-07-20 | 2015-12-02 | 浙江大学 | Methyl esterification recycling method of alkali decrement wastewater solid 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 |
| CN107963970A (en) * | 2016-10-19 | 2018-04-27 | 中国石化仪征化纤有限责任公司 | The recoverying and utilizing method of benzoic acid in slag and effluent |
| CN111643956A (en) * | 2020-05-27 | 2020-09-11 | 河北诚昊化工有限公司 | Device for purifying and saving raw materials by discharging pollution discharged from distillation kettle into buffer tank |
| WO2022156624A1 (en) * | 2021-01-20 | 2022-07-28 | 泰兴市福昌环保科技有限公司 | Production process for producing plasticizer from pta oxidation residue |
| CN116265044A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院大连化学物理研究所 | Method for treating paraxylene liquid phase oxidation residues |
-
2011
- 2011-09-30 CN CN2011103191473A patent/CN102516080A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103112968A (en) * | 2013-03-01 | 2013-05-22 | 山东潍坊润丰化工有限公司 | Method for treating high-COD (Chemical Oxygen Demand) components in phenoxyalkanoic acid production wastewater |
| CN103112968B (en) * | 2013-03-01 | 2014-09-10 | 山东潍坊润丰化工股份有限公司 | Method for treating high-COD (Chemical Oxygen Demand) components in phenoxyalkanoic acid production wastewater |
| US9714211B2 (en) | 2014-02-07 | 2017-07-25 | Lg Chem, Ltd. | Plasticizer and resin composition, and preparation method thereof |
| CN105102418A (en) * | 2014-02-07 | 2015-11-25 | Lg化学株式会社 | Plasticizers, resin composition, and method for manufacturing plasticizers and resin composition |
| CN110734579A (en) * | 2014-02-07 | 2020-01-31 | Lg化学株式会社 | Plasticizer, resin composition, and method for producing same |
| 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 |
| CN106187778B (en) * | 2015-05-06 | 2019-04-23 | 中国科学院大连化学物理研究所 | A method of processing o-Xylene Oxidation in Liquid Phase residue |
| CN105111074A (en) * | 2015-07-20 | 2015-12-02 | 浙江大学 | Methyl esterification recycling method of alkali decrement wastewater solid residue |
| CN105017022A (en) * | 2015-07-20 | 2015-11-04 | 浙江大学 | Method for methyl esterification recovery and recycle of PTA oxidation residue |
| CN107963970A (en) * | 2016-10-19 | 2018-04-27 | 中国石化仪征化纤有限责任公司 | The recoverying and utilizing method of benzoic acid in slag and effluent |
| CN111643956A (en) * | 2020-05-27 | 2020-09-11 | 河北诚昊化工有限公司 | Device for purifying and saving raw materials by discharging pollution discharged from distillation kettle into buffer tank |
| WO2022156624A1 (en) * | 2021-01-20 | 2022-07-28 | 泰兴市福昌环保科技有限公司 | Production process for producing plasticizer from pta oxidation residue |
| CN116265044A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院大连化学物理研究所 | Method for treating paraxylene liquid phase oxidation residues |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102516080A (en) | Recovery process of PX oxidation residues and recovery system device thereof | |
| CN103224260B (en) | Wastewater treatment and recovery method | |
| CN102267890B (en) | Method for extracting and recovering acrylic acid from acrylic ester production wastewater | |
| US20190127244A1 (en) | Method for producing acrylic ester with low pollutant discharge | |
| CN105001185A (en) | Maleic anhydride tail gas treatment equipment and maleic anhydride tail gas treatment process | |
| CN103044257B (en) | Terylene waste material produces alcoholysis method and the apparatus system of dioctyl terephthalate | |
| KR20210050511A (en) | System and method for rapid extraction and purification of ethyl acetate after compression esterification synthesis | |
| CN103012090B (en) | Method for recovering organic matters in polyester wastewater | |
| CN112851503A (en) | Comprehensive utilization process of PTA oxidation residues | |
| CN112876357A (en) | Production process for producing plasticizer from PTA oxidation residues | |
| CN101805263A (en) | Cleaning production method of phthalic acid di-(2-ethyl) ethyl ester | |
| CN109879471B (en) | COD (chemical oxygen demand) reduction treatment device and COD reduction treatment process for n-butyl acrylate neutralization wastewater | |
| CN110054336A (en) | Method for treating low-concentration acetic acid wastewater containing inorganic metal ions and organic impurities | |
| CN212102640U (en) | System for preparing acetic anhydride by acetic acid cracking-ketene method | |
| CN102350435A (en) | Novel process for treating indigo alkaline residue | |
| CN100999370A (en) | Treatment method of high alkalinity organic waste water | |
| CN203007176U (en) | Alcoholysis device system for preparing dioctyl terephthalate from Dacron wastes | |
| CN110437052A (en) | System and preparation method that acetaldehyde prepares acetic acid are recycled from esterification waste water | |
| CN108862432A (en) | A kind of preprocess method of high concentrated organic wastewater | |
| CN212757927U (en) | Environment-friendly device for recovering maleic anhydride from efficient solvent | |
| CN107986578A (en) | The biogas hydrogen manufacturing circulatory system and technique of a kind of PTA sewage disposals | |
| CN220183013U (en) | Energy-saving and environment-friendly PTA wastewater treatment device | |
| CN107673511A (en) | A kind of tower draws chinic acid recovery method in standby gallic acid waste liquid | |
| CN209173420U (en) | A kind of recyclable device for paint stripper waste liquid | |
| CN102059002A (en) | Method and device for purifying polyethylene glycol dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120627 |