CN1120747C - Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid - Google Patents
Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid Download PDFInfo
- Publication number
- CN1120747C CN1120747C CN99816661A CN99816661A CN1120747C CN 1120747 C CN1120747 C CN 1120747C CN 99816661 A CN99816661 A CN 99816661A CN 99816661 A CN99816661 A CN 99816661A CN 1120747 C CN1120747 C CN 1120747C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- oxidation catalyst
- described step
- filter
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4061—Regeneration or reactivation of catalysts containing metals involving membrane separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/74—Regeneration or reactivation of catalysts, in general utilising ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
-
- 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
-
- 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to an improved separation method for a continuous catalytic oxidation reaction of alkyl aromatic. The reaction is used for preparing aromatic carboxylic acid in a liquid solvent medium, wherein the liquid flow of reactor products is discharged from an oxidation process and is separated so as to generate liquid flow containing the products, mother liquor flow and purge flow containing catalyst. The purge flow subsequently flows through a filtering system (10) and a series of adsorption containers (30, 40, 50, 60) so as to remove the oxidation catalyst and separate impurities from the catalyst. A solvent is separated from reaction by-products by a traditional distillation method and is used in processes again, and reaction by-product residue is processed by calcining. The oxidation catalyst is eluted from an ion exchange column and is used in the processes again.
Description
Technical field
The oxidation catalyst that the present invention relates to be used for the manufacturing of aromatic carboxylic acid is removed and recovery method.More particularly, the present invention relates to the method with ion-exchange, from the living production fluid flow that contains some aromatic carboxylic acid the selective removal oxidation catalyst with separate unwanted impurity.The invention still further relates to method of purification, catalyst can be turned back in the oxidizing process the catalyst after reclaiming.In addition, the present invention also provides the recovery method of the economy of remaining aromatic acid " fines ", and the removal method of metal and foreign pigment.
Background technology
The autofrettage commonly used of aromatic carboxylic acid be under high-temperature and high-pressure conditions in liquid phase catalytic oxidation alkylaromatic hydrocarbon class.Be numbered 2,245,528; 2,833,816; 3,092,658 and 3,170,768 United States Patent (USP)s have disclosed the manufacture method example of aromatic carboxylic acid, and this paper all is incorporated herein by reference.Medium in the oxidation reactor generally comprises alkylaromatic hydrocarbon (aromatic alkyl), oxidation catalyst, oxygen-containing gas and solvent, and solvent generally is the lower aliphatic monocarboxylic acid.
The product liquid liquid stream of discharging from reactor also contains oxidation catalyst, solvent, oxidation reaction by-products and other process contaminants except containing aromatic carboxylic acid.Oxidation catalyst generally is made up of one or more kinds in cobalt, manganese and the hydrogen bromide.
Cooling products liquid stream, make the crystallization of product aromatic acid after, the aromatic carboxylic acid of major part is removed in the separation process of flowing through of reactor product liquid.Partition method commonly used is a centrifugal process.Mother liquor turns back to oxidation reactor then.The small portion of residual wash liquid stream that contains oxidation catalyst, small portion of residual aromatic carboxylic acid, byproduct of reaction, solvent and process contaminants is sent to separation process to reclaim solvent.This separation process produces the concentrated sludge that contains oxidation catalyst, byproduct of reaction and process contaminants.
Make very big effort and reached the purpose of from the aforementioned wash liquid stream that contains catalyst, removing impurity with traditional isolation technics.But all known methods of effectively removing impurity from give birth to production fluid flow but are unpractical technically, or are undesirable economically.These methods comprise chemical deposition or calcine the method for using the hydrometallurgical recovery catalyst then.The known method that makes spent ion exchange resin does not use upstream filtering technology to remove the small product particulate matter that can reduce the ion exchange resin function.
United States Patent (USP) 2,964,559 have disclosed a kind of method, and this method relates to by extracting catalyst with solvent from the bottomsstream, with the liquid phase oxidation reaction of recovery heavy metallic oxide catalyst.
United States Patent (USP) 3,341,470 have disclosed a kind ofly by liquid stream is calcined, and make various metals be converted into their oxide, reclaim the method for cobalt and Mn catalyst from oxidation mixtures, and with special reagent impurity are carried out selective chemical and precipitate.
United States Patent (USP) 3,873,468 have disclosed and have a kind ofly carried out the method that aqueous solution extraction carries out carbonate deposition then from stillage bottom.
United States Patent (USP) 3,959,449 have also disclosed a kind of method of carrying out aqueous solution extraction from stillage bottom, but be to pass through storng-acid cation exchange resin after this, solution is distilled, reclaim bromine, and reclaim heavy metal catalyst with the form of bromide with hydrobromic form.
United States Patent (USP) 4,162,991 have disclosed a kind of method that reclaims cobalt and bromide catalysts, this method be on strong-base anion-exchange resin adsoption catalyst, and come desorption cobalt and bromide ion with the lower aliphatic monocarboxylic acid.
United States Patent (USP) 4,546,202; 4,266,084; 4,258,227 and 4,393,264 have disclosed the method that reclaims catalyst from the pyrolysis ash.
Being numbered 4,855,491 United States Patent (USP) has disclosed and a kind ofly filters Sodium Benzoate with nanofilter but hold back the method for Co catalysts.
United States Patent (USP) 4,238,294 have disclosed a kind of method of using anion exchange resin to reclaim heavy metal ion and halogen valence state.The water concentration that disclosed method requires to give birth to production fluid flow is 20 weight % or still less.Disclosed method did not comprise any filtering technique of removing particulate matter before carrying out ion-exchange with anion exchange resin.
Summary of the invention
The present invention is a kind of removal, recovery and reuse oxidation catalyst and residual aromatic carboxylic acid, removes the improved continuity method of undesirable impurity simultaneously.
The invention provides a kind of improved separating technology of alkylaromatic hydrocarbon continuous catalysis oxidation reaction, this reaction is used for making aromatic carboxylic acid at the liquid flux medium.Wherein reactor product liquid stream is discharged from oxidizing process, produce the wash liquid stream that contains liquid stream, the mother liquor stream of product and contain catalyst through separating then, this wash liquid stream is removed oxidation catalyst through filtration system and a series of contactor subsequently, and from catalyst removing foreign matter.From byproduct of reaction, isolate solvent by traditional way of distillation then.Solvent is used in the flow process again, and byproduct of reaction residue or handle with traditional waste disposal method (as calcining) is perhaps sold on other market.In a preferred embodiment of the present invention, water wash-out oxidation catalyst from adsorbing medium; In another preferred implementation, then use strong inorganic acid, catalyst selectivity is precipitated out, after this catalyst is dissolved in the reaction dissolvent again.In first embodiment, the catalyst of the recovery anionic exchange medium of can flowing through then removes excessive bromide ion.Perhaps, after catalyst is by wash-out, can with catalyst selectivity be precipitated as carbonate or hydrate, filter drip washing, and in acetate, dissolve this precipitated catalyst after this more again.Available selective ion exchange resin removes the metal of sneaking into, as iron.Oxidation catalyst after the recovery has enough purity, can directly be used in oxidizing process again.
Oxidation catalyst in the mother liquor wash liquid stream that method of the present invention is suitable for producing making aromatic carboxylic acid by the alkylaromatic hydrocarbon liquid phase oxidation reaction is for recycling and reuse.This mother liquor wash liquid stream generally contains rudimentary aliphatic monocarboxylic acid, as the acetate as solvent; Benzoic acid and the higher condensed nucleus aromatic of other molecular weight as oxidation reaction by-products; Some unwanted aromatic carboxylic acid; Cobalt, manganese, hydrobromic acid and other trace metal reaction promoter as oxidation catalyst; With iron, chromium and other heavy metal as process corrosion impurity.
Hydrogen bromide is not being added in first preferred implementation of giving birth to production fluid flow, improved method comprises the following steps:
A) temperature with the mother liquor wash liquid stream keeps enough high, and preferred 50-100 ℃, so that aromatic acid is dissolved in the solution.Required temperature depends on the amount of aromatic acid and the byproduct of reaction of existence.
B) isolate remaining insoluble matter by high temperature filtration.Filter method is including, but not limited to traditional bag filter process or barrel type filtering method, cross-current membrane type filtration method, cross-flow microfiltration method, hyperfiltration method, centrifugal process and rotational flow separation method.Rotational flow separation method and centrifugal process are considered to be lower than other above-mentioned isolation technics in the effectiveness of removing on the fines.
C) temperature of afterreaction solvent is filtered in rising, and is preferably high 10 ℃ than mother liquor purge flow, is higher than the saturation temperature of solubility aromatic acid with the temperature that keeps solution.
D) make a series of cation exchange columns of solvent process that contain aromatic acid, byproduct of reaction, corrosion products and heavy metal oxidation catalyst, to remove heavy metal ion and corrosion products.
E) make the strong inorganic acid flow of solution through exchange column, from cation exchange resin column, remove heavy metal ion and corrosion products.
F) make a series of anion-exchange columns of solvent process that contain aromatic acid, byproduct of reaction, corrosion products and oxidation catalyst, remove bromide ion.
G) make the sodium hydroxide solution exchange column of flowing through, from the resin anion (R.A.) post, the bromide ion wash-out is come.
H) make solvent process granular active carbon (GAC) post that contains aromatic acid, byproduct of reaction, remove the condensed nucleus aromatic colour coupler of HMW.
I) make the caustic soda hot solution through GAC, remove the condensed nucleus aromatic compound.
J) by distillation, from reaction dissolvent, isolate aromatic acid and byproduct of reaction.
K) will be adjusted to 4-5 from the pH value of the acid solution of step (e),, and from acid solution, filter out the heavy metal hydroxide solid so that beavy metal impurity selective precipitation from oxidation catalyst comes out.Make flow of solution after the filtration through chelating ion exchange resin, remove remaining heavy metal residue, as copper, nickel and chromium.
L) with alkali metal salt (preferred hydroxide sodium or sodium carbonate) the pH value is adjusted to 8-10, so that be precipitated out from the oxidation catalyst residue of step (k) form with hydroxide or carbonate.
M) by filtering, isolate precipitated catalyst from the filtrate mother liquor, thoroughly any soluble-salt remaining in the filter cake is fallen in drip washing then.
N) the catalyst precipitation thing is dissolved in the reaction dissolvent of recovery again.
O) reaction dissolvent that makes the catalyst that contains dissolving is removed chloride or the sulfate ion of any remnants through resin anion (R.A.) post (preferred weak base type), then reaction dissolvent and catalyst is used in the oxidizing process again.
Hydrogen bromide is being added in second preferred implementation of giving birth to production fluid flow, and improved method comprises the following steps:
A) temperature with the mother liquor purge flow keeps enough high, preferred 50-100 ℃, aromatic acid is dissolved in the solution.Required temperature depends on the byproduct of reaction of aromatic acid amount and existence.
B), isolate remaining insoluble matter by high temperature filtration.Filter method is including, but not limited to traditional bag filter process or barrel type filtering method, cross-current membrane type filtration method, cross-flow microfiltration method, hyperfiltration method, centrifugal process and rotational flow separation method.
C) temperature of afterreaction solvent is filtered in rising, and is preferably high 10 ℃ than mother liquor purge flow, is higher than the saturation temperature of solubility aromatic acid with the temperature that keeps solution.
D) add hydrogen bromide (HBr) aqueous solution, its concentration is enough to form anion metal bromide complex with the metal oxidation catalyst ion.
E) make a series of anion-exchange columns of solvent process that contain aromatic acid, byproduct of reaction, corrosion products and heavy metal oxidation catalyst, remove heavy metal ion and corrosion products.
F) make current through ion exchange column, this measure is decomposed into corresponding metal cation and bromide ion with the metal bromide anionic complex, removes the heavy metal catalyst ion from the resin anion (R.A.) post.
G) from reaction dissolvent, remove remaining solubility aromatic acid and byproduct of reaction with traditional way of distillation.
H) make the flow through anionic exchange medium of " acetate " form of aqueous catalyst solution, from the catalyst that reclaims, remove any excessive bromide ion.Perhaps, making excessive bromide is carbonate or hydrate deposition, removes any excessive bromide ion from the catalyst that reclaims.
I) make the aqueous catalyst solution selectivity Ion Exchange Medium of flowing through, from the catalyst that reclaims, remove de-iron or other corrosion impurity.
Replacement scheme as these preferred implementations of the present invention, available continuous flow upstream ion-exchange is carried out identical ion exchange process, as use in this area the method for the pulsed-bed type that is called " John Higgins ring (Higgns Loop) ", or use the method for the continuous flow upstream revolving bed class that senior Separation Technologies, Inc. (Advanced SeparationsTechnology) makes.
Description of drawings
Fig. 1 is the process flow diagram of first preferred implementation of the present invention; Fig. 2 is the process flow diagram of second preferred implementation of the present invention.
The preferred forms of invention
Process chart among Fig. 1 is represented an embodiment of the invention.Though the present invention can change, the embodiment of Fig. 1 is a preferred implementation of the present invention.But the content that shown in Figure 1 and the present invention describes in detail should think to be example of the present invention, rather than to the restriction of the specific embodiment shown in Figure 1.
Referring to Fig. 1, it has shown a kind of embodiment, and this embodiment is a kind of method of utilizing principle of the invention recovery and reuse oxidation catalyst from the processing and manufacturing liquid stream that contains aromatic carboxylic acid.
Reaction dissolvent liquid stream that a part contains product is flowed through flow to filtration system 10 by conduit 12.The insoluble granule material is removed by system 10 from reaction dissolvent liquid stream.Insoluble substance is including, but not limited to the product aromatic carboxylic acid, as terephthalic acids (TA), because its solubility in reaction dissolvent is limited.Preferred filtration system is a cross-current membrane type filter, and it is made by pottery or sintering metal alloy material.But,, then also be suitable for if the aperture of miscellaneous equipment is small enough to the basic all particulates matter of removing from reaction dissolvent.Suitable miscellaneous equipment comprises pocket type, cartridge type or tubular filter.Also require filter method will comprise the device that the product aromatic acid of catching on the filter medium is removed continuously, to prevent the hole of aromatic acid blocking filtering medium.For this reason, cross-current membrane type filtration method is desirable.Another kind of suitable filtering method is the filter of being made by Funda company, and it uses the filter medium level to pile up plate and wiper arm is removed captive product continuously.Though bag filter has the required ability of product fines of catching, it also has the shortcoming that cost is high and the product that is hunted down is easily piled up.Cross-current membrane type filter comprises ceramic filter and sintered metal filter, all has corrosion-resistant and resistant to elevated temperatures advantage.Preferred operating temperature is 35-100 ℃, is more preferably 50-100 ℃.
Cross-current membrane type filter plant relies on the backflow of purge flow to prevent that the hole of filter medium from stopping up.The effect of filter medium is to concentrate purge flow, and the concentrated purge flow of the solvent that contains product is discharged from filter plant continuously.Stop up in order to prevent the filter hole, the speed that requires liquid stream to pass filter medium will keep enough height, just turbulent flow can make granular solids remain on suspended state like this.The Reynolds (Reynold's) criterion of liquid that enters cross-current membrane type filter fluid passage has been found that if approximately greater than 13,000, just can obtain suitable turbulent flow.The ratio of the shear stress that the power that Reynolds (Reynold's) criterion is defined as mass flow and viscosity cause.It is the dimensionless number that calculates with following formula:
Re=Dv ρ/μ wherein
D is a caliber
V is a fluid velocity
ρ is a fluid density
μ is absolute fluid viscosity.
Reaction dissolvent liquid after filtration stream 22 heat exchanger 20 of flowing through, this heat exchanger can be elevated to the temperature of reaction dissolvent preferred operating temperature, and is promptly high 10 ℃ than the temperature of mother liquor purge flow.Intensification makes the temperature of reaction dissolvent be kept above the saturation temperature of the aromatic acid of dissolving.
Reaction dissolvent flows through ion exchange resin (IER) container 30 via conduit 32.Container 30 is removed solubility oxidation catalyst and other trace metal corrosion products, as iron, nickel and chromium.Preferred IER is a strong acidic ion resin.Optionally the IER medium can be ResinTech CG8, Rohm﹠amp; Haas IR-120, Ionac C-249, Purolite C-100 or homologue.When the IER medium exhausts fully, promptly when the hydrogen ion on the IER medium fully and metal ion when displacement, with water wash IER container, remove remaining reaction dissolvent.Make strong acid aqueous solution flow through container 30, from the IER medium, remove oxidation catalyst and trace metal via conduit 34.Acid is hydrogen ion with metal replacement.The strong acid that is suitable for the IER regenerative process is including, but not limited to hydrochloric acid, hydrobromic acid and sulfuric acid.Washing water is removed remaining metallic acid via conduit 34, and flows to catalysis purification process 70 via conduit 36.
Reaction dissolvent flows through IER container 40 via conduit 42.Container 40 is as " refining " container.Container 40 is removed the remaining oxidation catalyst that container 30 is not removed.The purpose that " refining " container 40 required to reach is to make container 30 obtain maximal efficiency and prevent that any oxidation catalyst is lost to the reaction dissolvent removal process.Preferred IER is a strong acidic ion resin.Optionally the IER medium can be ResinTech C68, Rohm ﹠amp; Haas IR-120, Ionac C-249, Purolite C-100 or homologue.When the IER medium exhausts fully, promptly when the hydrogen ion on the IER medium fully and metal ion when displacement, with water wash IER container, remove remaining reaction dissolvent.Make strong acid aqueous solution flow through container 40, from the IER medium, remove oxidation catalyst and trace metal via conduit 44.Acid is hydrogen ion with metal replacement.The strong acid that is suitable for the IER regenerative process is including, but not limited to hydrochloric acid, hydrobromic acid and sulfuric acid.Washing water is removed remaining metallic acid via conduit 44, and enters catalyst purification process 70 via conduit 46.
Reaction dissolvent flows through IER container 50 via conduit 52.Container 50 is removed the free bromine ion that is present in the reaction dissolvent.Preferred IER is weak anion resin (gel resin or a macroreticular resin).Optionally the IER medium can be ResinTech WBMP, Rohm﹠amp; Haas IR68, Ionac AFP-329, PuroliteA-100, Dow WGR-2 or homologue.When the IER medium exhausts fully,, remove remaining reaction dissolvent with water wash container 50.Make strong alkali aqueous solution flow through container 50 then, from the IER medium, remove bromide ion via conduit 54.Strong alkali solution acid is replaced into hydroxide ion with bromide ion.The highly basic that is suitable for the IER regenerative process is including, but not limited to NaOH or potassium hydroxide.
Reaction dissolvent flows through container 60 via conduit 62.Container 60 contains granular active carbon (GAC).The condensed nucleus aromatic quality compound that GAC absorbing molecules amount is higher.If remaining aromatic carboxylic acid will be recovered as the raw material that is used for other market, just need remove the quality compound.Product such as polyalcohol, resin and plasticizer that the residue that reclaims can be made.The caustic soda hot solution flows through container 60 via conduit 64, removes the condensed nucleus aromatic compound.The preferred temperature of soda lye is 50-150 ℃.The preferred concentration of soda lye is 1-20%.
Reaction dissolvent after the processing flows to the acetate removal process via conduit 68, isolates reaction dissolvent from the aromatic acid of remnants.Reaction dissolvent turns back in the oxidizing process.The aromatic acid that reclaims has enough purity, can be as the raw material of selling in the aforesaid market.
The inorganic acid of oxidation catalyst, heavy metal corrosion products and regeneration is via conduit 36 and 46 inflow catalyst purification process 70.With strong alkali aqueous solution come neutralizing acid solution to pH be 4-5.Highly basic for example but be not limited to NaOH or potassium hydroxide, they are the nertralizers that are suitable for.Beavy metal impurity is precipitated as the metal hydroxides sludge.Flow of solution after the neutralization is removed sludge particles through filter.The filter of any kind all is suitable for, as long as its aperture is small enough to remove granular heavy metal sludge.Suitable device is pocket type, cartridge type, plate/frame (plate/frame) and tubular type cross-flow filter.Oxidation catalysis agent solution after the filtration can flow through chelating ion exchange resin, removes remaining heavy metal, as copper, nickel and chromium.The chelating ion exchange resin that is suitable for comprises the polystyrene resin that has amino oxalic acid functional group, as Sybron SR-5, Rohm$Haas IR718 or Resintech SIR300.Oxidation catalysis agent solution after the filtration flows into oxidation catalyst conversion process 80 via conduit 82.
Soluble carbon hydrochlorate, bicarbonate or hydroxide add via conduit 84, make the oxidation catalyst of being made up of cobalt and manganese be precipitated as hydrate, carbonate or bicarbonate.The anion that provides the precipitation of gold metal catalyst required all is provided any compound, as sodium carbonate, sodium acid carbonate or NaOH.The pH value of solution should be adjusted to 8.5-9.5.Filter the Co/Mn slurries with filter, filter preferably can be isolated the board-like and frame filter press of Co/Mn solid from salting liquid.Other suitable filter comprises horizontal leaf filter, the model of being made by Funda company for example, or the sintering metal tubulose filter of being made by Mott Usiminas.With the thorough drip washing filter cake of demineralized water, remove soluble-salt.Make the reaction dissolvent (acetate) of recovery flow through filter, the Co/Mn catalyst dissolution in reaction dissolvent, is dissolved fully until filter cake via conduit 86.Filter liquor goes to carry out waste disposal via conduit 88.Filter liquor generally contains the sodium salt or the sylvite of inorganic acid; For example sodium chloride or potassium sulfate.
Cobalt acetate/manganese solution flows through IER container 90 via conduit 92.Container 90 contains weakly-basic anion IER medium, and this medium can be removed the inorganic anion of any trace, for example but be not limited to chloride or or sulfate.Cobalt acetate/manganese solution turns back in the oxidizing process by conduit 98.
Make strong alkali aqueous solution pass through conduit 94, remove inorganic anion, make the IER cleaning of medium.Be suitable for making the highly basic of the IER cleaning of medium including, but not limited to NaOH.Via conduit 96, go to carry out waste disposal by the sodium salt that regeneration produced of IER medium.
Following table has shown the effect example of aforesaid catalyst recovery process and content shown in Figure 1:
Table 1
Utilize ion exchange resin from synthesis reaction solvent, to remove catalyst
Composition charging IER flows out liquid acetate, % 95 95 water, % 55 cobalts, PPM (PPM) 1,100＜1 manganese, PPM 200＜1 charging rates, ml/min 20 temperature, ℃ 49 49 resinous type sulfonated polystyrene-resin volume, milliliter 400-acetate volume, milliliter 12,400-
The data of table 1 have illustrated that clearly the sample that utilizes prepared in laboratory can remove effectively to cobalt/Mn catalyst.
Referring to Fig. 2, it has shown second kind of embodiment, and this embodiment is to utilize principle of the present invention, the method for recovery and reuse oxidation catalyst from the production and processing liquid stream that contains aromatic carboxylic acid.
The acetate wash liquid stream that contains oxidation catalyst flows into filtration system 110 via pipeline 112.Insoluble aromatic acid is removed by system 110 from reaction dissolvent liquid stream.The main component of insoluble matter comprises the aromatic carboxylic acid product, because its solubility in reaction dissolvent is limited.Residual solution stream (retentate stream) 115 turns back to the aromatic acid product and cleans in the feeder trough.Come the anhydrous discharge currents of self-cleaning feeder trough then to turn back in the aromatic acid manufacturing process.Preferred filtration system is a cross-current membrane type filter plant.The preferred structure material of cross-flow filter is pottery or sintered powder metal alloy.But,, then also be suitable for if the aperture of other filter plant is small enough to remove substantially all particulates matter in the reaction dissolvent.The method that removes particulate matter with filtration is a preferable methods, though other method also is suitable for, so ineffective.An example is upwards to flow through the adsorbing medium that particle can be passed through.Other filter plant that is suitable for comprises pocket type, cartridge type, tubular filter and centrifugation apparatus.Preferred operating temperature is 35-120 ℃, is more preferably 50-100 ℃.
Acetate purge flow 122 flows through heat exchanger 120, and heat exchanger 120 is elevated to preferred operating temperature with the temperature of reaction dissolvent, promptly is higher than the temperature of 10 ℃ of feeding liquid streams.Intensification makes the temperature of liquid be kept above the saturation temperature of the aromatic acid of dissolving.
Make hydrobromic acid (HBr) aqueous solution inject acetate purge flow 132 via pipeline 135, to form the anion bromide complex of cobalt and manganese respectively with enough stoichiometric proportions.Adsorbing medium can be by any composition the in some anion exchange resin.Anionic exchange medium can be a strong base, also can be the weak base type.Optionally anionic exchange medium can be the highly basic class, for example but be not limited to Sybron ASB1, also can be the weak base class, for example but be not limited to Rohm and Haas IRA67.The preferred anionic surfactants exchange media is a pyridine radicals anion exchange resin, for example but be not limited to Reillex HP or HPQ.Other Ion Exchange Medium based on the pyridine chemistry also is suitable for.Make the flow of solution that contains bromide ion cross medium, make the anion adsorbing medium be converted into the bromide form.Preferred solution is hydrobromic acid (HBr), because it generally is the part of oxidative system.
Acetate purge flow 132 flows through the contactor 130 that contains the anion adsorbing medium.Container 130 is removed the oxidation catalyst as anion metal bromide complex.The acetate that flows out from container 130 flows through the refining vessel 140 that contains this anion adsorbing medium equally via pipeline 142.Carry out suction-operated completely in the container 130 to such degree, make the catalyst concn that flows out in the liquid be at least in the acetate purge flow catalyst concn 50%.Use refining vessel 140 that the adsorbing medium in the container 130 is maximized the use, and prevent the loss of oxidation catalyst.
The outflow liquid of container 140 flows to container 145 via pipeline 143.Container 145 is removed and is present in the bromide ion that flows out in the liquid.Preferred IER is weak anion resin (gel resin or a macroreticular resin).Optionally the IER medium can be ResinTech WBMP, Rohm﹠amp; Haas IR68, Ionac AFP 329, PuroliteA-100, Dow WGR-2 or homologue.When the IER medium exhausts,, remove remaining reaction dissolvent with water wash container 145.Make strong alkali aqueous solution flow through container 145 then, from the IER medium, remove bromide ion.Strong base solution is replaced into hydroxide ion with bromide ion.The highly basic that is suitable for regenerative process is including, but not limited to NaOH or potassium hydroxide.
The outflow liquid of container 145 flows in the acetate removal process via pipeline 144, and this process is isolated acetate from the aromatic acid of remnants.The back acetate of will purifying then turns back in the oxidizing process.
An optional step in the catalyst recovery process is that the outflow liquid that makes container 145 flows through the container 150 that contains granular active carbon (GAC) via pipeline 144.It is colour former that GAC removes the higher condensed nucleus aromatic of molecular weight.The outflow liquid of GAC container flows to the acetate removal process via pipeline 152.The acetate that reclaims turns back in the oxidizing process.The enforcement of this processing procedure is shown in embodiment 4.Remaining aromatic series after the purification has the economic worth as the pure and mild unsaturated polyester resin raw material of polyester polyols.By first water, use caustic soda heat (70-90 ℃) solution (5-10%) drip washing GAC then, can make GAC regeneration.The higher aromatic series of molecular weight is removed from GAC, and handles in traditional ecological waste treatment system as soluble sodium salt.
Make water flow through adsorbing medium, from container 130 wash-out oxidation catalysts via pipeline 136.The anion metal complex of cobalt and manganese is destroyed in the presence of water, forms their respective metal cation and bromide ion.Use the water management elution process, thereby the catalyst solution that obtains concentrating (4-5% metal) flows to container 170 via 138 then.In final elution step, contained cobalt and manganese concentration relatively low (＜5,000 PPM) in the water.This " tail washings (tail) " flows to container 160 via pipeline 137, and is used in next catalyst wash-out process again via pipeline 162.By utilizing wash-out " tail washings " again, the maximum organic efficiency of oxidation catalyst can reach more than 98%.
If the catalyst that reclaims contains too much water, can randomly use traditional Reverse Osmosis Technology that water is infiltrated from catalyst.
The contained bromide ion of the oxidation catalyst that reclaims is excessive with respect to the general required metal of oxidizing process and the ratio of bromide.Make catalyst solution flow through the container 180 that contains anion exchange resin via pipeline 172, remove this excessive bromide ion in the catalyst of recovery, this anion exchange resin for example but be not limited to IRA67, Purolite 845 or Sybron ASB1.Resin anion (R.A.) can be the weak base type, also can be strong base, but the preferred anionic surfactants resin is the weak base type.Anion IER is the acetate form, and it makes the acetate ion of equivalent be replaced into the bromide ion of equivalent.The outflow liquid of removing the container 180 of bromide uses in the container 170 via pipeline 182 again.When the ratio of metal and bromide reaches right value, utilize process to stop again, and the remainder catalyst in the container 180 clean in the container 170 with acetate.
Perhaps, do not use ion exchange process, but be carbonate or hydrate, can remove excessive bromide ion yet the bromide selective precipitation.Then the bromide behind the filtering-depositing, drip washing, and be dissolved in the acetate again.
Residual acetic acid cleans in the container 170 with demineralized water.Use conventional ion exchange method of reproduction then, make Ion Exchange Medium regeneration with the caustic soda aqueous solution.Make acetic acid aqueous solution flow through container 170 subsequently, make resin anion (R.A.) be converted into the acetate form.Ion exchange resin is removed to circulate for bromide next time and is got ready then.
The catalysis adsorption process provides the effective recovery to cobalt and manganese, and metal protection impurity (as nickel and cobalt) is flow through, and enters the acetate removal process.Yet iron can be accumulated in the catalyst solution of recovery, but can make the catalyst solution of recovery flow to container 190 from container 170 via pipeline 176 as corrosion impurity, removes de-iron.Container 190 contains selective Ion Exchange Medium, and it can be in the existence of cobalt and the manganese deironing of going down.The selectivity Ion Exchange Medium for example can be but be not limited to Resintech SIR-500, Rohm﹠amp; HaasIR-718, Purolite S-950 or Eichrome Eiphonix.Preferred selective resin is the strong acidic ion resin of being made by Eichrome industrial group that contains pyrophosphoric acid functional group.The catalyst that reclaims flows through container 190 via pipeline 176, and 190 pairs of iron of container carry out selective removal.Oxidation catalyst after purifying then turns back in the oxidizing process via pipeline 192.
Make the solution of dense inorganic acid flow through container 190, make the selectivity IER regeneration in the container 190 via pipeline 196.Inorganic acid for example but be not limited to hydrochloric acid, hydrobromic acid and sulfuric acid.Preferred acid is hydrochloric acid.With in the alkali chemical (as lime or caustic soda) and ferric chloride solution, make its precipitation.Handle iron mud with rational method then.Another kind of renovation process is with rare hydrobromic acid aqueous solution drip washing container 190, and this method can be removed any remaining cobalt of chemical replacement to the selective resin of understanding.The HBr concentrated solution that preferably contains 25-48%HBr can flow through the selective resin in the container 190.The iron of removing from selective resin is converted into anion bromide complex in the presence of dense HBr.By making the anion IER of flow of solution perbromide form, can remove the ferric bromide anionic complex.The water wash-out is removed ferric bromide, and dense HBr is reused in the regenerative process next time of container 190.Available then traditional intermediate processing is handled iron.The cobalt that reclaims can be used in again and reclaim in the catalyst storage tank.After the regeneration, with the IER medium in the thorough drip washing container 190 of deionized water.
The enforcement of aforementioned oxidation catalyst removal process and content shown in Figure 1 is shown in following embodiment:
Embodiment:
Embodiment 1
Resinous type: strong alkalinity anion
Resin manufacture factory: Sybron chemical company
Resin specification: ASB1
Describe: the crosslinked polystyrene that has quaternary amine functional group
Resin bed volume: 100 milliliters
Flow velocity: 4BV/ hour
Temperature: environment temperature
Catalyst behind the analysis-weight PPM incoming flow fluid wash-out
Co 486 0 10,500
Mn 485 3.7 5,970
Fe 2 0 14
Ni 3 0 13
Cr 7 3.9 12.5
Br 3,200 17,250
Embodiment 2
Resinous type: weakly-basic anion
Resin manufacture factory: Rohm and Haas company
Resin specification: IRA 67
Describe: the crosslinked acrylic resin that has tertiary amine functional group
Resin bed volume: 100 milliliters
Flow velocity: 4BV/ hour
Temperature: environment temperature
Catalyst behind the analysis-weight PPM incoming flow fluid wash-out
Co 486 1.5 5,120
Mn 485 9.1 2,070
Fe 2 3.4 37
Ni 3 .6 4
Cr 7 5.05 5
Br 3,200 25,500
Embodiment 3
Resinous type: in strong/weakly alkaline anion
Resin manufacture factory: Reilly industrial group
Resin specification: HPQ
Describe: the crosslinked polyethylene yl pyridines that has chloromethyl season functional group
Resin bed volume: 100 milliliters
Flow velocity: 4BV/ hour
Temperature: environment temperature
Catalyst behind the analysis-weight PPM incoming flow fluid wash-out
Co 486 0 57,900
Mn 485 0 28,300
Fe 2 0 102
Ni 3 0 91
Cr 7 2.7 107
Br 3,200 30,850
The foregoing description explanation by the present invention, can easily reach removal and recovery to oxidation catalyst.This paper explanation and describe method be from the acetate purge flow, to reclaim oxidation catalyst, from catalyst, remove corrosion metal contaminants then, and remove excessive bromide ion.The oxidation catalyst that reclaims has met or has surpassed the process specification of making good oxidation catalyst.
Excessive water may influence the effectiveness of ion exchange resin in the mother liquor purge flow.Therefore water content is preferably approximately less than 20%.By recovered solvent is used in the mother liquor purge flow again, make the water content of mother liquor purge flow be maintained at about 20% or still less, just can address this problem.
Industrial applicibility
Because to be a large amount of various aromatic carboxylic acid products of various uses manufacturing at present, and the used catalyst material cost height of this manufacture process, so people wish to provide a kind of low cost method to come the recovery and reuse oxidation catalyst.The present invention provides the significant improvement that surmounts present method method by expensive catalyst material being carried out effectively and economically reclaim for utilizing again.Also need a kind of separation method, this separation method can effectively separate and reclaim insoluble aromatic acid product, and from remaining purge flow, remove oxidation catalyst economically, and with catalyst recovery with use oxidizing process again, and unwanted impurity is stayed in the remaining purge flow.Another economic benefit of the present invention is, remaining aromatic acid in the further purification purge flow, can make the manufacturer of aromatic acid from remaining aromatic acid, obtain some economic worths, and these remaining aromatic acids are running off at present in the technology via waste treatment process.
Though describe the present invention and describe with reference to the specific embodiment, therefore the present invention is not restricted.These are to optional improvement of the present invention, and this is tangible to having read previously described those skilled in the art.Therefore, need only these optional changes and improvement in the purpose and scope of described claim, they just should be considered part of the present invention.
Claims (36)
1. the method for recovery and reuse oxidation catalyst and aromatic carboxylic acid's product the mother liquor purge flow that when the alkylaromatic hydrocarbon liquid phase oxidation prepares the aromatic carboxylic acid, produces, described mother liquor purge flow contains the lower aliphatic monocarboxylic acid as solvent; Oxidation reaction by-products; Aromatic carboxylic acid; Cobalt, manganese, hydrobromic acid and trace metal as oxidation catalyst; With iron, chromium and other heavy metal, it is characterized in that this method comprises the steps: as corrosion by-products
A) by the described mother liquor purge flow of filter media, the insoluble aromatic carboxylic acid of recovery and reuse and other insoluble matter;
B) make the described solvent streams that contains aromatic acid, byproduct of reaction, corrosion products and heavy metal oxidation catalyst through a series of ion exchange columns, remove heavy metal oxidation catalyst and corrosion by-products;
C) described oxidation catalyst of wash-out and heavy metal corrosion by-products from described ion exchange column;
D) temperature with described mother liquor purge flow keeps enough high, is dissolved in the solution to keep described aromatic acid; And under this high temperature, carry out the filter process of step a);
E) before step b), the temperature of the described filtration afterreaction solvent that raises is higher than the saturation temperature of solubility aromatic acid with the temperature that keeps this solution;
F) make the strong inorganic acid flow of solution through described ion exchange column, carry out the elution process of step c);
G) make the described solvent streams that contains aromatic acid, byproduct of reaction, corrosion by-products and oxidation catalyst through a series of anion-exchange columns, to remove excessive bromide ion;
H) make the sodium hydroxide solution described ion exchange column of flowing through, with wash-out bromide ion from described anion-exchange column;
I) be the GAC post by making the described solvent streams that contains aromatic acid and byproduct of reaction through granular active carbon, to remove the condensed nucleus aromatic colour former of HMW;
J) make the caustic soda hot solution described granular active carbon of flowing through, from this granular activated charcoal, to remove described condensed nucleus aromatic compound;
K) by distillation, from reaction dissolvent, to isolate described aromatic acid and byproduct of reaction;
L) be adjusted to 4-5 by pH value, described beavy metal impurity optionally is precipitated out from described oxidation catalyst, and from described acid solution, filter out the hydroxide solids of described heavy metal the described acid solution of step f);
M) acid solution after the described filtration is flowed through chelating resin is to remove remaining heavy metal the acid solution after filtering;
N) with alkali salt the pH value is adjusted to 8-10, from step (m) remaining oxidation catalyst is precipitated out with the form of hydroxide or carbonate, and, from filtrate, isolate the described catalyst of precipitation by filtering, drip washing goes out the salt of any residual dissolving from filter cake then;
O) described catalyst precipitation thing is dissolved in the reaction dissolvent of described recovery again; And the catalyst that makes this reaction dissolvent and the dissolving resin anion (R.A.) post of flowing through together, chlorion or sulfate ion to remove any remnants utilize reaction dissolvent and catalyst into oxidizing process then again.
2. the method for claim 1, the filter process that it is characterized in that described step a) also comprise the insoluble aromatic carboxylic acid that continuous recovery and reuse are caught and the step of other insoluble matter from filter medium.
3. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the hyperfiltration medium.
4. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the microfiltration medium.
5. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the membrane filtration medium.
6. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with crossflow filtration media.
7. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the spinning liquid filter medium.
8. method as claimed in claim 6 is characterized in that the filter process of described step a) carries out with cross-current pottery microfiltration medium.
9. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the bag filtration medium.
10. method as claimed in claim 2 is characterized in that the filter process of described step a) carries out with the accumulation formula filter that wiper arm is housed, and removes continuously piling up insoluble aromatic carboxylic acid and other insoluble matter of catching on the formula filter.
11. method as claimed in claim 6 is characterized in that the filter process of described step a) carries out with sintering metal cross-stream micro-filtration medium.
12. method as claimed in claim 8, the filter process that it is characterized in that described step a) comprises makes described mother liquor purge flow circular flow cross the cross-flow microfiltration medium, stops up to prevent the cross-stream micro-filtration medium.
13. method as claimed in claim 12 is characterized in that keeping circulating of described mother liquor purge flow being enough to keep to be at least under the flow conditions of 13,000 Reynolds (Reynold's) criterions.
14. the method for claim 1 is characterized in that the filter process barrel type filtering method of described step a).
15. the method for claim 1 is characterized in that the filter process of described step a) uses the cross-stream micro-filtration method.
16. the method for claim 1 is characterized in that the filter process hyperfiltration method of described step a).
17. the method for claim 1 is characterized in that the hydroxide in the described step (n) is NaOH.
18. the method for claim 1 is characterized in that the carbonate in the described step (n) is sodium carbonate.
19. the method for claim 1 is characterized in that the resin anion (R.A.) post in the described step (o) is the weak base type.
20. the method for claim 1 is characterized in that carrying out continuous flow upstream type ion exchange process in the ion exchange column of described step (b).
21. method as claimed in claim 20 is characterized in that described continuous flow upstream type ion exchange process is the pulsed-bed type.
22. method as claimed in claim 20 is characterized in that described continuous flow upstream type ion exchange process is a continuous flow upstream revolving bed type.
23. the method for claim 1 is characterized in that it also comprises the steps, promptly adds hydrogen bromide (HBr) aqueous solution, its concentration is enough to form anion metal bromide complex with described metal oxidation catalyst ion;
By making current through described ion exchange column, carry out the elution process of step c), this water-washing step destroys the metal bromide anionic complex and is corresponding metal cation and bromide ion;
From described reaction dissolvent, remove remaining solubility aromatic acid and byproduct of reaction with the conventional way of distillation;
Make the flow through anionic exchange medium of " acetate " form of described aqueous catalyst solution, from the catalyst of this recovery, to remove excessive bromide ion;
Make the described aqueous catalyst solution selectivity Ion Exchange Medium of flowing through, from the catalyst of this recovery, remove de-iron or other corrosive impurity;
The wash-out tail washings (tail) that produces in the elution process to step (c) utilizes again.
24. method as claimed in claim 23 is characterized in that the filter process bag filter process of described step a).
25. method as claimed in claim 23 is characterized in that the filter process barrel type filtering method of described step a).
26. method as claimed in claim 23 is characterized in that the filter process cross-flow microfiltration method of described step a).
27. method as claimed in claim 23 is characterized in that the filter process hyperfiltration method of described step a).
28. method as claimed in claim 23, the ion exchange column that it is characterized in that described step b) is a pyridine type.
29. the method for claim 1 is characterized in that the oxidation catalyst of described recovery contains excessive bromide ion, described method also comprises with the oxidation catalyst of this recovery anion exchange resin of flowing through, to remove the step of excessive bromide ion.
30. the method for claim 1 is characterized in that it also comprises the steps, is about to recovered solvent and is used in the described mother liquor purge flow again, with the excessive water in the dilution mother liquor purge flow.
31. method as claimed in claim 30 is characterized in that water content in the described mother liquor purge flow remains on 20% or still less.
32. the method for claim 1 is characterized in that the ion exchange column in the described step b) is a strongly basic anionic resin, this resin comprises the crosslinked polystyrene that has quaternary amine functional group.
33. the method for claim 1 is characterized in that the ion exchange column in the described step b) is a weak anion resin, this resin comprises the crosslink propylene acid resin that has tertiary amine functional group.
34. the method for claim 1 is characterized in that the ion exchange column in the described step b) is a strong acidic ion resin, this resin comprises the polystyrene of sulfonation.
35. the method for claim 1, it is characterized in that ion exchange column in the described step b) be in strong/weak anion resin, this resin comprises the polyvinylpyridine that has chloro methyl season functional group.
36. the method for claim 1 is characterized in that the oxidation catalyst of described recovery contains excessive water, described method also comprises the step that water is infiltrated with reverse osmosis from the oxidation catalyst that reclaims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1999/018729 WO2001012318A1 (en) | 1999-08-17 | 1999-08-17 | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1359313A CN1359313A (en) | 2002-07-17 |
| CN1120747C true CN1120747C (en) | 2003-09-10 |
Family
ID=22273403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99816661A Expired - Fee Related CN1120747C (en) | 1999-08-17 | 1999-08-17 | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1224029A4 (en) |
| JP (1) | JP2003507160A (en) |
| KR (1) | KR20020046280A (en) |
| CN (1) | CN1120747C (en) |
| AU (1) | AU5490899A (en) |
| MX (1) | MXPA02001652A (en) |
| WO (1) | WO2001012318A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237385A (en) * | 2006-03-01 | 2016-01-13 | 奇派特石化有限公司 | Versatile oxidation byproduct purge process |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362442A (en) | 1993-07-22 | 1994-11-08 | 2920913 Canada Inc. | Method for sterilizing products with gamma radiation |
| US6696060B2 (en) | 2001-06-14 | 2004-02-24 | Clearant, Inc. | Methods for sterilizing preparations of monoclonal immunoglobulins |
| US7252799B2 (en) | 2001-08-31 | 2007-08-07 | Clearant, Inc. | Methods for sterilizing preparations containing albumin |
| US6749851B2 (en) | 2001-08-31 | 2004-06-15 | Clearant, Inc. | Methods for sterilizing preparations of digestive enzymes |
| KR100715024B1 (en) * | 2005-02-18 | 2007-05-09 | 삼성석유화학(주) | The recovery process for catalyst from wastewater in the purification of terephthalic acid |
| CN100348508C (en) * | 2005-07-27 | 2007-11-14 | 上海东化环境工程有限公司 | Treatment technology of acrylic acid waste water |
| CN101395121A (en) * | 2006-03-01 | 2009-03-25 | 伊士曼化工公司 | Versatile oxidation byproduct purge process |
| ATE403636T1 (en) * | 2006-06-12 | 2008-08-15 | Hyosung Corp | DEVICE AND METHOD FOR RECOVERING ACETIC ACID AND CATALYST IN A PRODUCTION PROCESS OF NAPHTHALINE-2,6-DICARBONIC ACID |
| US7396457B2 (en) | 2006-06-27 | 2008-07-08 | Hyosung Corporation | Apparatus and method for recovering acetic acid and catalyst in process for preparation of 2,6-naphthalenedicarboxylic acid |
| US20100016629A1 (en) | 2006-12-11 | 2010-01-21 | Mitsubishi Gas Chemical Company, Inc. | Process for production of terephthalic acid |
| CN101553455B (en) | 2006-12-20 | 2013-01-09 | 三菱瓦斯化学株式会社 | Process for production of isophthalic acid |
| KR101467603B1 (en) * | 2007-05-31 | 2014-12-01 | 다우 이탈리아 에스.알.엘. | Process for the recovery of oxidation catalyst using ion exchange resins |
| JP2009091610A (en) * | 2007-10-05 | 2009-04-30 | Nippon Filter Kk | Method for purifying waste treatment liquid for chemical conversion film of trivalent chromium |
| TWI402277B (en) * | 2007-12-31 | 2013-07-21 | Ind Tech Res Inst | Method of forming an adsorptive ion-exchange material |
| CN102199082B (en) * | 2010-03-26 | 2016-08-17 | 英威达技术有限公司 | Aromatic carboxylic acids and the recovery of oxidation catalyst |
| ES2769630T3 (en) * | 2010-10-26 | 2020-06-26 | Mitsubishi Gas Chemical Co | Cross flow type filtration method of operation using a ceramic filter |
| SG189999A1 (en) * | 2010-10-26 | 2013-06-28 | Mitsubishi Gas Chemical Co | Crossflow type filtering operation method using ceramic filter |
| JP6644633B2 (en) * | 2015-08-07 | 2020-02-12 | Ｊｆｅケミカル株式会社 | Method for producing dicyclopentadiene-modified phenolic resin |
| WO2017127650A1 (en) * | 2016-01-21 | 2017-07-27 | Archer Daniels Midland Company | Methods of recovering catalysts |
| CN109019959A (en) * | 2018-08-09 | 2018-12-18 | 中国电子系统工程第二建设有限公司 | A kind of processing unit of strong complex state heavy metal wastewater thereby and its discharge and reuse technology |
| CN111533683B (en) * | 2020-05-27 | 2023-05-09 | 鹤壁市赛科化工有限公司 | Method and device for preparing vinyl pyridine by continuous dehydration of hydroxyethyl pyridine |
| CN115591588B (en) * | 2021-07-07 | 2024-03-26 | 中国石油化工股份有限公司 | Method for recovering liquid phase oxidation catalyst |
| WO2023021347A1 (en) * | 2021-08-20 | 2023-02-23 | Koch Technology Solutions UK Limited | Nickel and cobalt separation in a pta process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB899288A (en) * | 1957-07-31 | 1962-06-20 | Standard Oil Co | Process for the removal of bromine anions or bromine anions and heavy metal cations from solutions comprising a lower saturated monocarboxylic acid |
| GB1595904A (en) * | 1977-04-25 | 1981-08-19 | Ici Ltd | Recovery catalyst values |
| JPS54133495A (en) * | 1978-04-10 | 1979-10-17 | Asahi Chem Ind Co Ltd | Recovering method for liquid phase oxidation catalyst |
| DE4034501A1 (en) * | 1990-10-30 | 1992-05-07 | Hoechst Ag | METHOD FOR REMOVING METAL CORROSION PRODUCTS FROM WATER-FREE CARBONYLATION REACTIONS |
| KR100321476B1 (en) * | 1995-01-07 | 2002-07-31 | 에스케이 주식회사 | Method for regenerating oxidizing catalyst for use in fabrication of trimellitic acid |
| SG72858A1 (en) * | 1997-09-09 | 2000-05-23 | Mitsubishi Gas Chemical Co | Process for producing aromatic carboxylic acid |
-
1999
- 1999-08-17 JP JP2001516655A patent/JP2003507160A/en active Pending
- 1999-08-17 CN CN99816661A patent/CN1120747C/en not_active Expired - Fee Related
- 1999-08-17 AU AU54908/99A patent/AU5490899A/en not_active Abandoned
- 1999-08-17 WO PCT/US1999/018729 patent/WO2001012318A1/en not_active Application Discontinuation
- 1999-08-17 KR KR1020027001991A patent/KR20020046280A/en not_active Application Discontinuation
- 1999-08-17 EP EP99941213A patent/EP1224029A4/en not_active Withdrawn
- 1999-08-17 MX MXPA02001652A patent/MXPA02001652A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237385A (en) * | 2006-03-01 | 2016-01-13 | 奇派特石化有限公司 | Versatile oxidation byproduct purge process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003507160A (en) | 2003-02-25 |
| CN1359313A (en) | 2002-07-17 |
| KR20020046280A (en) | 2002-06-20 |
| EP1224029A4 (en) | 2004-09-08 |
| AU5490899A (en) | 2001-03-13 |
| WO2001012318A1 (en) | 2001-02-22 |
| EP1224029A1 (en) | 2002-07-24 |
| MXPA02001652A (en) | 2002-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1120747C (en) | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid | |
| US5955394A (en) | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acids | |
| JP4788023B2 (en) | Method for recovering catalyst components from liquid phase oxidation reaction mother liquor | |
| CN101928089B (en) | Method for disposing antiosmosis thick water out of purified terephthalic acid refined waste water | |
| CN101254985B (en) | PTA refined mother liquor reclaiming method and system | |
| TW201026613A (en) | Process for the treatment of waste water generated in an aromatic acid production process | |
| EP0164402B1 (en) | Recovery of organic acids, catalysts and water from terephthalic acid manufacture | |
| CN110818149A (en) | PTA refining mother liquor recovery method and recovery system | |
| KR101892075B1 (en) | Apparatus for treating brine discharged from desalination process of sea water | |
| KR100459530B1 (en) | Process for the purification of wash water from the production of aromatic acids | |
| CN102199109B (en) | Preparation method of isophorone nitrile | |
| CN1233975A (en) | Catalyst recovery | |
| US7314954B1 (en) | System and method for recovering PTA mother liquid and purifying and regenerating of catalyst | |
| WO2010066181A1 (en) | Simple method and system for recycling mother liquor of pta apparatus efficiently | |
| US5980750A (en) | Process for the purification of waste wash water | |
| CN1315295A (en) | Process for treating waste water generated in production of refined terephthalic acid | |
| CN105517987B (en) | The method of recycle-water, metal and organic matter from the production of polybasic carboxylic acid | |
| CN101177394A (en) | Crude terephthalic acid (CTA) residue recovery and catalyst purification regeneration system and method | |
| CN101745410B (en) | Method for recycling catalyst from waste water produced in purifying process of aromatic acids | |
| KR20180096560A (en) | Apparatus for treating brine discharged from desalination process of sea water | |
| JPS61500553A (en) | Washing water treatment method during terephthalic acid production | |
| WO2023021347A1 (en) | Nickel and cobalt separation in a pta process | |
| KR100930229B1 (en) | Recovery of aromatic acid, catalyst and high purity water from wastewater of aromatic acid purification process | |
| JP4065726B2 (en) | Method for producing heavy metal-containing catalyst | |
| JPH04342549A (en) | Production of aminocarboxylic acid salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030910 Termination date: 20090917 |