CN110105196A - The recovery method of terephthalic acid (TPA) - Google Patents
The recovery method of terephthalic acid (TPA) Download PDFInfo
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- CN110105196A CN110105196A CN201910507559.6A CN201910507559A CN110105196A CN 110105196 A CN110105196 A CN 110105196A CN 201910507559 A CN201910507559 A CN 201910507559A CN 110105196 A CN110105196 A CN 110105196A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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Abstract
The present invention relates to a kind of recovery methods of terephthalic acid (TPA), comprising steps of terephthalic acid (TPA) salting liquid is made in terephthaldehyde's acid waste products；Prepare the active powdered carbon of carrying transition metal；Active powdered carbon, terephthalic acid (TPA) salting liquid and strong oxidizer are subjected to catalytic oxidation；Filter activity powdered carbon simultaneously flocculates to gained filtrate；Filtering flocculation liquid, and using multistage film separation system to its stage purification；By purified filtrate acid out, until forming suspension；Suspended things are crushed, isolated terephthaldehyde's acid deposit is filtered；Cleaning, drying crushes terephthaldehyde's acid deposit, obtains terephthalic acid (TPA) product.Recovery method of the invention makes the terephthalic acid (TPA) product of recycling have high-purity, and the quality more than Grade A with national Specification in conjunction with catalysis oxidation and film separation coupling technique.
Description
Technical field
The present invention relates to changing rejected material to useful resource field, in particular to a kind of recovery method of terephthalic acid (TPA).
Background technique
Terephthalic acid (TPA) (PTA) is a kind of important chemical industry raw material, in its production and the use of its derived product
In the process, a large amount of industrial waste can be generated, the alkali generated such as the pond material, the chemical fibre dyeing that generate in PTA production process
It is reduced waste material etc..Such waste material quality is low, directly larger using difficulty；Difficult for biological degradation, direct emission will cause biggish ring
Border pollution；When by the methods of burning processing, not only air easy to pollute, but also result in waste of resources.Purifying to such waste material
Just become certainty.
The Chinese invention patent application of Publication No. CN101121655 discloses a kind of purifying work of crude terephthalic acid
Skill: than investment container and clear water stirring is added by 3/10 solid water, wait stir in the crude terephthalic acid that will be recycled in dyeing waste water first
Started to warm up after mixing uniformly, and being uniformly added into concentration is 18~27% ammonium hydroxide or carbonic acid hydrogen ammoniums, the pH value to solution 8 or more,
60~95 DEG C of ranges are warming up to, keep the temperature 20~50 minutes, terephthalic acid (TPA) is reacted completely and generates terephthalic acid (TPA) ammonium；Filtering pair
Phthalic acid ammonium hot solution removes insoluble solid finely ground particles；Then filtrate is cooled to 10 DEG C hereinafter, being precipitated to benzene two
Ammonium formate crystal, filtering or centrifugation removing soluble impurity, obtain white needles terephthalic acid (TPA) ammonium crystal；It finally will be to benzene two
Ammonium formate crystal is put into vacuum drying decomposer, within the scope of 120~180 DEG C, 2~6 hours, is dehydrated and makes terephthalic acid (TPA)
Ammonium resolves into terephthalic acid (TPA) and ammonia, and gained terephthalic acid (TPA) purity is up to 98% or more.Ammonia returns to dissolution after absorbing and uses.
The invention is to achieve the purpose that imurity-removal using the method for crystalline terephthalic acid's salt, and process energy consumption is higher.
The Chinese invention patent of Publication No. CN 1680261 discloses a kind of method of purification of crude terephthalic acid, the party
Alkali decrement waste water is mainly obtained terephthalic acid (TPA) by method after acid out precipitates, and further by its ball milling, makes terephthalic acid (TPA) grain
Diameter reaches 1~5 μm；Then 60 DEG C -100 DEG C at a temperature of, dipping centrifuge separation obtains the relatively high terephthaldehyde of purity
Sour finished product, impurity content are lower than 0.5~1.5%.The characteristic of the invention is that crude terephthalic acid washes leaching through hot water again
Stain improves the purity of terephthalic acid (TPA) to greatest extent, and technique is simpler, but the water-insoluble impurity of heat not can be removed, and cause most
Finished product purity cannot be stablized 99% or more.
The Chinese invention patent of Publication No. CN 104710300B discloses one kind extraction pair from terephthalic acid residue
The method of phthalic acid.Crude terephthalic acid is crushed with pulverizer, is placed in a small amount of water, solid-liquid suspension is formed, hydrogen is added
Sodium hydroxide solution dissolves suspended particulate.The mixture of ferric trichloride and polyacrylamide is added thereto again, by suspended matter mistake
Filter.Trimethyl dihydroquinoline polymer powder is added thereto, adds dilute hydrochloric acid, and filters pressing will be precipitated with filter press.Gained
Sediment is dried through acetone washing again.For this method using crude terephthalic acid as raw material, the terephthalic acid (TPA) purified is pure
Degree is up to 99.5%.The invention final products purity is higher, but need to use a variety of inorganic and organic medicament, and medicament is difficult to benefit again
With processing cost is higher.
The Chinese invention patent application of Publication No. CN101041616 discloses the side that terephthalic acid (TPA) is purified from waste material
Method, this method first wash terephthalic acid (TPA) or Alkali reduction waste material, form suspension, add alkaloid compound, filter
Filtrate is obtained, composite finishing agent is then added in filtrate, refilters to obtain filtrate；Acid compounds acid is added in filtrate
Change, the terephthalic acid (TPA) of acid precipitation is washed again, and terephthaldehyde's acid content after dehydration and drying can reach 98%, then again
Double solvents is being added, is dissolving it at a temperature of 110-120 DEG C and forms saturated solution, terephthaldehyde's acid crystals is precipitated in decrease temperature crystalline
Body adds alcohol and is washed, and after filtration drying, the purification of terephthalic acid product that content is 99.5% or more can be obtained.It should
It is long to invent the process route proposed, needs to consume alkali compounds, finishing agent, double solvents, acid compound, alcohol etc.
Medicament, higher cost.
In the purifying of terephthaldehyde's acid waste products, the quality of above-mentioned patented technology treated terephthalic acid (TPA) is relatively
Low, wherein the primary quality measure such as content, color etc. of application market concern, is not achieved the requirement of industrial primes, value is not
Height can only be used as low side raw material.It can be reprocessed using oxidation technology to improve quality.But it uses and directly throws
The method for oxidation oxidation time for entering oxidant is long, and oxidation of impurities is not thorough, and needs to heat to promote to react.But once add
Heat, side reaction increase, and oxidant consumption increases substantially, and product yield reduces, and the still difficult requirement for reaching industrial primes.
Summary of the invention
The purpose of the present invention is in order to solve the above problem, the present invention provides a kind of product purity 99.7% or more, and produces
Product quality reaches the terephthalic acid (TPA) that Grade A requires in GB/T 32685-2016 " industrial pure terephthalic acid PTA " standard
Purification treating method.
According to the present invention, a kind of recovery method of terephthalic acid (TPA) is provided, comprising the following steps: by terephthaldehyde's acid waste products
Terephthalic acid (TPA) salting liquid is made；Prepare the active powdered carbon of uniform load transition metal；By the active powdered carbon of carrying transition metal
It is placed in terephthalic acid (TPA) salting liquid, and strong oxidizer is added and carries out using transition metal as the catalytic oxidation of catalyst；Instead
After answering, filter activity powdered carbon adds sulfuric acid aluminum flocculation to decoloration in filtrate；Filtering flocculation liquid, obtained filtrate is sent
The purification of excess of imports membrane separation system；By purified filtrate acid out, until forming the suspension that pH value is 3-4；Ultrasonic agitation is extremely
The suspended things of suspension are broken, then filter separation, obtain terephthaldehyde's acid deposit；Terephthaldehyde's acid deposit is cleaned, is dried
Dry grinding obtains terephthalic acid (TPA) product.
Wherein, it is 15 DEG C -25 DEG C that catalytic oxidation step, which includes: the temperature of catalytic oxidation, is stirred to react 1-2h.
Wherein, catalytic oxidation step includes: the active powdered carbon of carrying transition metal, terephthalic acid (TPA) salting liquid and strong
The ratio range of oxidant are as follows: 2-5g:1000-1500ml:1-10ml.
Wherein, the step of preparing the active powdered carbon of carrying transition metal includes: to prepare the transition metal that concentration is 5%-8%
Sulfate liquor；The pH value of transition metal sulfate solution is adjusted to 4-5；Active powdered carbon is put into the salting liquid while stirring
In, suspension is formed, 15 DEG C -25 DEG C of temperature control, carries out transition metal salt in the load of active powdered carbon；After load, filter
Sediment；It by drying precipitate, toasts, be ground to 100 mesh, obtain the active powdered carbon of carrying transition metal.
Wherein, the step of preparing terephthalic acid (TPA) salting liquid include: by terephthaldehyde's acid waste products under conditions of base excess
It is dissolved in water, pH value is controlled 7~9；It filters and separates insoluble impurity, obtained filtrate is terephthalic acid (TPA) salting liquid.
Wherein, in UF membrane purifying step, it is 1000-30000 grades that Ultra filtration membrane system, which includes at least molecular cut off,
Other film separation system.
Wherein, in flocculation step, the proportion of aluminum sulfate and filtrate is 0.2g:1500ml.
Wherein, strong oxidizer includes the hydrogen peroxide that concentration is 30%；Transition metal includes iron, nickel, manganese, cobalt, terephthaldehyde
Acid waste products includes the production waste material and printing and dyeing white clay of p-phthalic acid；Active powdered carbon is living using charcoal matrix activated carbon, coconut husk base
Property charcoal or bamboo charcoal matrix activated carbon.
The present invention have it is following the utility model has the advantages that
1, product quality is high, has a wide range of application.Product reaches national standard GB/T 32685-2016 " industrial essence terephthaldehyde
Sour PTA " in high-class product and Grade A requirement, it is applicable in the occasion that p-phthalic acid is applicable in.
2, medicine consumes low, high income.Method Chinese medicine type provided by the present invention is few, and is inorganic medicament, cheap,
It is easy to buy, effectively saves medicine consumption, overall cost is lower than chemically synthesized terephthalic acid (TPA).
3, safety is higher.Using room temperature, being run under normal pressure, reaction condition is mild, and it is lower to equipment requirement, it operates simultaneously
It is safer more reliable.
4, adaptation range is stronger.To the pond waste material and dyeing generated in p-phthalic acid (PTA) production process
Alkali reduction white clay and other field generate terephthaldehyde's acid waste products can purify.
Specific embodiment
The illustrative embodiments of the disclosure will be more fully described according to embodiment below.Although being shown in specification
The illustrative embodiments of the disclosure, it being understood, however, that may be realized in various forms the disclosure without that should be illustrated here
Embodiment limited.It is to be able to thoroughly understand the disclosure on the contrary, providing these embodiments, and can incite somebody to action
The scope of the present disclosure is fully disclosed to those skilled in the art.
It is right to industrial essence that the purity of the terephthalic acid (TPA) of method recycling of the invention meets national standard GB/T 32685-2016
The technical requirements of phthalic acid (PTA).Below by by way of specific embodiment, technical solution of the present invention is done into one
Walk explanation.
Embodiment 1
(1) ferrous sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；It while stirring will be active
Carbon powder is put into solution, and 15-25 DEG C of temperature control, after 1.5h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning
Filter cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.Active carbon is cooled to room temperature, and is ground to 100 mesh and is waited for
With.
(2) terephthaldehyde's acid waste products (printing and dyeing white clay) 80g (content 80-96%), NaOH 40g is taken to put into 1500ml clear water
In, stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 2-3ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the reaction was completed, the active carbon filtered out in mixed liquor makes mixed liquor decolourize.After the completion of decoloration, delay while stirring
Slowly the solution that the aluminum sulfate containing 0.2g is added into filtrate flocculates, and stirs at low speed 20min, filters separation flocculation liquid.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane.
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get siccative
69.2g。
Through measuring, this rate of recovery 86.5%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 2
(1) nickel sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
100 mesh are stand-by.
(2) terephthaldehyde's acid waste products (printing and dyeing white clay) 80g (content 80-96%), NaOH 40g is taken to put into 1500ml clear water
In, stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 2-3ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane.
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product 70g.
Through measuring, this rate of recovery is 87.5%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 3
(1) manganese sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
It is stand-by after 100 mesh.
(2) terephthaldehyde's acid waste products (printing and dyeing white clay) 80g (content 80-96%), NaOH 40g is taken to put into 1500ml clear water
In, stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 2-3ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane.
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product
70.2g。
Through measuring, this rate of recovery 87.75%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 4
(1) cobaltous sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
It is stand-by after 100 mesh.
(2) terephthaldehyde's acid waste products (printing and dyeing white clay) 80g (content 80-96%), NaOH 40g is taken to put into 1500ml clear water
In, stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 2-3ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product 68g.
Through measuring, this rate of recovery 85%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 5
(1) ferrous sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；It while stirring will be active
Carbon powder is put into solution, and 15-25 DEG C of temperature control, after 1.5h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning
Filter cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, grind
It is stand-by after to 100 mesh.
(2) terephthaldehyde's acid waste products (pond material) 80g (content 70-90%), NaOH 40g is taken to put into 1500ml clear water,
Stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 3-4ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get siccative
62.5g。
Through measuring, this rate of recovery 78.5%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 6
(1) nickel sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
It is stand-by after 100 mesh.
(2) terephthaldehyde's acid waste products (pond material) 80g (content 70-90%), NaOH 40g is taken to put into 1500ml clear water,
Stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 2g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 3-4ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 1000-5000 filters, and collects the clear liquid for penetrating ultrafiltration membrane
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product
63.2g。
Through examining, this rate of recovery 79%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 7
(1) manganese sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
It is stand-by after 100 mesh.
(2) terephthaldehyde's acid waste products (pond material) 80g (content 70-90%), NaOH 40g is taken to put into 1000ml clear water,
Stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 5g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 1-2ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 10000-30000 filters, and collects the clear liquid for penetrating ultrafiltration membrane
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product
63.8g。
Through measuring, this rate of recovery 79.8%, terephthalic acid (TPA) total acid content > 99.7% of recycling.
Embodiment 8
(1) cobaltous sulfate is dissolved in water, forms the solution that concentration is 5%, adjust pH value of solution to 4-5；While stirring by active carbon
Powder is put into solution, and 15-25 DEG C of temperature control, after 1h, reaction terminates.The suspension is filtered, active carbon forms filter cake, cleaning filter
Cake.Filter cake after cleaning is sent into convection oven, 150 DEG C, toasts 4h.After 4h, takes out active carbon and be cooled to room temperature, be ground to
It is stand-by after 100 mesh.
(2) terephthaldehyde's acid waste products (pond material) 80g (content 70-90%), NaOH 40g is taken to put into 1000ml clear water,
Stirring and dissolving 2-3h is filtered after the reaction was completed and is separated insoluble impurity, and filtrate is collected stand-by.
(3) the carrier 3g of step (1) preparation is added in filtrate, is slowly added to 30% hydrogen peroxide of 8-10ml in stirring, controls
15-25 DEG C of temperature, it is stirred to react 1h.
(4) after the completion of decolourizing, the solution that the aluminum sulfate containing 0.2g is slowly added into filtrate while stirring flocculates, low speed
20min is stirred, separation flocculation liquid is filtered.Filtrate uses multi-ultrafiltration to handle again, collects the clear liquid for penetrating ultrafiltration membrane.
(5) the hollow fiber ultrafiltration membrane equipment that filtrate first passes through that aperture is 100nm filters, and filtered fluid is again through molecular cut off
The hollow fiber ultrafiltration membrane equipment of 10000-30000 filters, and collects the clear liquid for penetrating ultrafiltration membrane
(6) sulfuric acid acid out is slowly added in clear liquid, it is stirring while adding.When solution ph reaches 3, stop acid adding, after
It is continuous to stir and with after ultrasonication sediment 30min, it filters and separates.
(7) filter cake is cleaned with pure water.
(8) filter cake that cleaning finishes is sent into baking oven, dries 5h under conditions of vacuum and 120 DEG C of temperature to get finished product
62.6g。
Through measuring, this rate of recovery 78.3%, terephthalic acid (TPA) total acid content content > 99.7% of recycling.
Comparative example
Keep other recycling conditions same as Example 1, the temperature for changing catalytic oxidation is 10 DEG C, mixing time
For 5h, the proportion of the active powdered carbon of carrying transition metal, terephthalic acid (TPA) salting liquid and strong oxidizer is 9g:1500ml:10ml
The recovery processing of phthalic acid is carried out again.
Through measuring, this recycles this rate of recovery 74%, the terephthalic acid (TPA) total acid content ﹤ 88.1% of recycling.
Testing result
Standard detection is carried out to above-described embodiment and recording a demerit for comparative example, and judges whether qualification referring to national standard, is had
Body result is as shown in the table.
According to upper table result, the finished product of terephthalic acid (TPA) made of embodiment 1,4,5,6,7,8 meets national standard first-class
The requirement of product, the finished product of terephthalic acid (TPA) made of embodiment 2,3 meets the requirement of national standard high-class product, and produces made of comparative example
Object does not meet national standard.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of the claim
Subject to enclosing.
Claims (8)
1. a kind of recovery method of terephthalic acid (TPA), which comprises the following steps:
Terephthalic acid (TPA) salting liquid is made in terephthaldehyde's acid waste products；
Prepare the active powdered carbon of uniform load transition metal；
The active powdered carbon, terephthalic acid (TPA) salting liquid and strong oxidizer of carrying transition metal are mixed, progress is with transition metal
The catalytic oxidation of catalyst；
After reaction, filter activity powdered carbon obtains colorless filtrate, and so that colorless filtrate is flocculated with aluminum sulfate；
Filtering flocculation liquid, and it is sent to Ultra filtration membrane system purification；
The filtrate of purification is subjected to acid out, until forming the suspension that pH value is 3-4；
The suspended things of broken suspension, then filter isolated terephthaldehyde's acid deposit；
Cleaning, drying crushes terephthaldehyde's acid deposit, obtains terephthalic acid (TPA).
2. recovery method as described in claim 1, which is characterized in that catalytic oxidation step includes:
The temperature of catalytic oxidation is 15 DEG C -25 DEG C, and being stirred to react the time is 1-2h.
3. recovery method as described in claim 1, which is characterized in that catalytic oxidation step includes:
The ratio range of the active powdered carbon of carrying transition metal, terephthalic acid (TPA) salting liquid and strong oxidizer is 2-5g:1000-
1500ml:1-10ml。
4. recovery method as described in claim 1, which is characterized in that the step of preparing the active powdered carbon of carrying transition metal packet
It includes:
Prepare the transition metal sulfate solution that concentration is 5%-8%；The pH value of transition metal sulfate solution is adjusted to 4-
5；Active powdered carbon is put into the salting liquid while stirring, suspension is formed, 15 DEG C -25 DEG C of temperature control, carries out transition metal salt and exist
The load of active powdered carbon；After load, sediment is filtered to obtain；It by drying precipitate, toasts, be ground to 100 mesh, loaded
The active powdered carbon of transition metal.
5. recovery method as described in claim 1, which is characterized in that the step of preparing terephthalic acid (TPA) salting liquid include:
Terephthaldehyde's acid waste products is dissolved in water under conditions of base excess, pH value is controlled 7~9；
It filters and separates insoluble impurity, obtained filtrate is terephthalic acid (TPA) salting liquid.
6. recovery method as described in claim 1, which is characterized in that
In UF membrane purifying step, Ultra filtration membrane system includes at least the UF membrane that molecular cut off is 1000-30000 rank
System.
7. recovery method as described in claim 1, which is characterized in that
Strong oxidizer includes the hydrogen peroxide that concentration is 30%；Transition metal includes iron, nickel, manganese, cobalt, and terephthaldehyde's acid waste products includes
The production waste material and printing and dyeing white clay of p-phthalic acid；Active powdered carbon uses charcoal matrix activated carbon, coconut shell based activated carbon or bamboo charcoal
Matrix activated carbon.
8. recovery method as described in claim 1, which is characterized in that
In flocculation step, the proportion of aluminum sulfate and filtrate is 0.2g:1500ml.
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