CN115591588B - Method for recovering liquid phase oxidation catalyst - Google Patents
Method for recovering liquid phase oxidation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000007791 liquid phase Substances 0.000 title claims abstract description 86
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 73
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 239000003463 adsorbent Substances 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 28
- -1 polysubstituted alkyl arene Chemical class 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000011084 recovery Methods 0.000 claims abstract description 21
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 84
- 239000002245 particle Substances 0.000 claims description 59
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 56
- 238000005243 fluidization Methods 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 26
- 238000004064 recycling Methods 0.000 claims description 23
- GWLLTEXUIOFAFE-UHFFFAOYSA-N 2,6-diisopropylnaphthalene Chemical compound C1=C(C(C)C)C=CC2=CC(C(C)C)=CC=C21 GWLLTEXUIOFAFE-UHFFFAOYSA-N 0.000 claims description 21
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 238000004062 sedimentation Methods 0.000 claims description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 6
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims description 6
- CJJFFBINNGWEBO-UHFFFAOYSA-N 2,6-diethylnaphthalene Chemical compound C1=C(CC)C=CC2=CC(CC)=CC=C21 CJJFFBINNGWEBO-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 38
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 30
- 239000011572 manganese Substances 0.000 description 17
- 239000008247 solid mixture Substances 0.000 description 17
- 229910052794 bromium Inorganic materials 0.000 description 15
- 229940011182 cobalt acetate Drugs 0.000 description 15
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 15
- 229940071125 manganese acetate Drugs 0.000 description 15
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 15
- 229940094035 potassium bromide Drugs 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 14
- 239000007790 solid phase Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
-
- 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
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/56—Hydrocarbons
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for recovering a liquid phase oxidation catalyst, which comprises the following steps: (1) The polysubstituted alkyl arene is contacted and reacted with an oxidation catalyst in an organic solvent to obtain a solid-liquid mixture; (2) And (3) contacting the solid-liquid mixture with an adsorbent, and separating to obtain a liquid phase containing an organic solvent and a catalyst, the adsorbent and a reactant polysubstituted carboxyl aromatic hydrocarbon, wherein the oxidation catalyst contains metal and halogen atoms. According to the recovery method of the liquid-phase oxidation catalyst, the product obtained by the oxidation reaction is directly contacted with the adsorbent, so that the purposes of simultaneously recovering the catalyst solution and decoloring the oxidation product are achieved. Not only simplifying the recovery flow of the catalyst and realizing the recovery and reutilization of the oxidation catalyst, but also carrying out preliminary purification on the product and obtaining better technical effect.
Description
Technical Field
The invention relates to the field of catalyst recovery, in particular to a method for recovering a liquid phase oxidation catalyst.
Background
The 2,6-NDA is usually obtained by a liquid phase oxidation method of 2, 6-dialkyl naphthalene, acetic acid is used as a solvent, air or oxygen is used as an oxidant, and a catalyst in the oxidation process is Co-Mn-Br. The method comprises the routes of 2, 6-dimethylnaphthalene (2, 6-DMN) liquid phase oxidation, 2, 6-diethylnaphthalene liquid phase oxidation and 2, 6-diisopropylnaphthalene liquid phase oxidation.
The 2,6-DMN liquid phase oxidation route is developed and researched by Amoco company (which is purchased by Bp), the reaction is carried out at 193-213 ℃ and 1-3Mpa, and the catalyst is Co-Mn-Br salt. The mass ratio of the solvent to the 2,6-DMN is 3-6, mn: co (molar ratio) is 2.5-4, br (Co+Mn) (molar ratio) is 0.4-0.7, wherein when the addition amount is too small, the oxidation reaction rate is too slow, the content of colored byproducts is increased, and when the addition amount is too large, the brominated byproducts are increased. However, the raw material 2,6-DMN is difficult to obtain and has poor economy. 2, 6-diisopropylnaphthalene is another reaction raw material for liquid phase oxidation, however, it was found that under the same reaction conditions as 2,6-DMN, the yield of the product obtained by oxidizing 2, 6-diisopropylnaphthalene was less than 50%, and the purity of the product was also low. Even with the same catalyst usage, the yield of the oxidation process is not increased to the desired value either with a two-step oxidation reaction or at lower raw material concentrations. In order to increase the yield of 2,6-NDA, the catalyst concentration of the reaction system should be increased. The catalyst dosage is approximately 100 times of the dosage of the 2,6-DMN oxidation process. For any oxidation process, the recycling of the catalyst is critical, especially for a 2, 6-diisopropylnaphthalene oxidation system, and the reasonable catalyst recycling route directly influences the economy of the whole process due to the huge catalyst consumption.
In the conventional 2,6-NDA decoloring method, a substance to be decolored is dissolved in a solvent and then decolored by using a decoloring agent. However, 2,6-NDA has only a certain solubility in strong polar solvents (such as azodicarbonamide, dimethyl sulfoxide, etc.), and has low solubility (solubility of less than 12% at 100 ℃), and a large amount of organic solvent is consumed by the conventional decoloring method.
In summary, no report on efficient catalyst recycling in the oxidation process of 2, 6-dialkyl naphthalene is found in the prior literature and patent.
Disclosure of Invention
The invention aims to solve the technical problem of huge catalyst consumption in the preparation process of polysubstituted alkyl aromatic hydrocarbon in the prior art, and provides a recovery method of a liquid phase oxidation catalyst, which can simplify the recycling flow of the oxidation catalyst.
The invention provides a method for recovering a liquid phase oxidation catalyst, which comprises the following steps:
(1) The polysubstituted alkyl arene is contacted and reacted with an oxidation catalyst in an organic solvent to obtain a solid-liquid mixture;
(2) And (3) contacting the solid-liquid mixture with an adsorbent, and separating to obtain a liquid phase containing an organic solvent and a catalyst, the adsorbent and a reactant polysubstituted carboxyl aromatic hydrocarbon, wherein the oxidation catalyst contains metal and halogen atoms.
Preferably, the method comprises: and (3) recycling the liquid phase containing the organic solvent and the catalyst as a reaction material in the step (1).
Preferably, the contacting and separating in the step (2) are carried out simultaneously in a device I, wherein the device I comprises a large-particle fluidization section I, a small-particle fluidization section II and a solid sedimentation section which are communicated from bottom to top, and the solid sedimentation section is positioned at the joint of the large-particle fluidization section I and the small-particle fluidization section II;
preferably, a discharge port is arranged at the bottom of the solid sedimentation section and used for flowing out the adsorbent, a liquid-solid mixing discharge port is arranged at the small-particle fluidization section II and used for flowing out the polysubstituted carboxyl aromatic hydrocarbon and the liquid phase containing the catalyst, and the liquid phase containing the catalyst after solid-liquid separation is used for oxidization recycling;
preferably, the solid-liquid mixture and the adsorbent enter and contact from the bottom of the large-particle fluidization section I, then the organic solvent containing the catalyst and the polysubstituted carboxyl aromatic hydrocarbon flow out from a liquid-solid mixing discharge port of the small-particle fluidization section II, and the adsorbent flows out from a discharge port of the solid sedimentation section.
Preferably, the angle α of the junction is <70 °, preferably 30 ° to 60 °.
Preferably, the bed diameter of the large-particle fluidization section I is 0.1 to 0.8 times, preferably 0.1 to 0.5 times, the bed diameter of the small-particle fluidization section II.
Preferably, the bed height of the large-particle fluidization stage I is 1.5 to 10 times, preferably 1.5 to 5 times, the bed height of the small-particle fluidization stage II.
Preferably, the operating temperature of the apparatus I is from 0 to 200 ℃.
Preferably, the contacting of step (2) is performed in a batch still and then the separation is performed in a solid-liquid separation device, which is one or more of a pressure filtration device, a centrifugal device and a sedimentation device.
Preferably, the metal of the oxidation catalyst is Co and/or Mn, and the halogen atom is Br.
Preferably, the organic solvent is one or more of aliphatic carboxylic acids, preferably C1-C6 carboxylic acids, preferably acetic acid.
Preferably, the polysubstituted alkylaromatic hydrocarbon is polysubstituted alkylbenzene and/or polysubstituted alkylnaphthalene; the polysubstituted alkylbenzene is one or more of paraxylene, o-xylene, m-xylene, meta-trimethylbenzene and durene, and the polysubstituted alkylnaphthalene is dialkyl naphthalene at any substituted position, preferably one or more of 2, 6-dimethylnaphthalene, 2, 6-diethylnaphthalene and 2, 6-diisopropylnaphthalene.
Preferably, the adsorbent is one or more of molecular sieve, activated carbon and activated alumina, preferably activated carbon, more preferably granular activated carbon.
Preferably, the adsorbent is used in an amount of 0.1 to 50wt%, preferably 1 to 20wt% based on the mass of solids in the solid-liquid mixture.
Preferably, the total content of the oxidation catalyst in the organic solvent is not more than 20wt%.
According to the recovery method of the liquid-phase oxidation catalyst, the product obtained by the oxidation reaction is directly contacted with the adsorbent, so that the purposes of simultaneously recovering the catalyst solution and decoloring the oxidation product are achieved. Not only simplifying the recovery flow of the catalyst and realizing the recovery and reutilization of the oxidation catalyst, but also carrying out preliminary purification on the product and obtaining better technical effect.
Drawings
Fig. 1 is a device I according to a preferred embodiment of the invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for recovering a liquid phase oxidation catalyst, which comprises the following steps:
(1) The polysubstituted alkyl arene is contacted and reacted with an oxidation catalyst in an organic solvent to obtain a solid-liquid mixture;
(2) And (3) contacting the solid-liquid mixture with an adsorbent, and separating to obtain a liquid phase containing an organic solvent and a catalyst, the adsorbent and a reactant polysubstituted carboxyl aromatic hydrocarbon, wherein the oxidation catalyst contains metal and halogen atoms.
The catalyst recycling method has the advantages of simple recycling scheme and decoloring the products obtained by oxidation.
According to one embodiment of the invention, the liquid phase comprising the organic solvent and the catalyst is preferably recycled as reaction mass for step (1). The catalyst recycling method has the advantages of simple recycling scheme and decoloring the products obtained by oxidation.
According to one embodiment of the present invention, the oxidation catalyst contains both metal and halogen atoms, which can be recovered by the method of the present invention, and according to a preferred embodiment of the present invention, preferably the metal of the oxidation catalyst is Co and/or Mn, the halogen atom is Br, and more preferably the oxidation catalyst contains Co, mn and Br, in a molar ratio of the three of 0.1-10:1:1-10.
Oxidation catalysts meeting the aforementioned requirements, such as a mixture of cobalt acetate, manganese acetate and potassium bromide, in which Co: mn: the molar ratio of Br is 0.1-10:1:1-10, for example, the examples are as follows: mn: the Br molar ratio is 0.5:1:1 as an exemplary illustration.
The catalyst having the foregoing catalyst composition can be recovered by the method of the present invention.
According to one embodiment of the invention, the organic solvent is one or more of aliphatic carboxylic acids, preferably C1-C6 carboxylic acids, such as formic acid, acetic acid, etc., more preferably acetic acid. According to the present invention, by using the organic solvent, colored impurities in the product are continuously dissolved and adsorbed on the adsorbent, thereby obtaining the effect of decoloring and recovering the catalyst-containing organic solvent.
According to one embodiment of the invention, the polysubstituted alkylaromatic hydrocarbon is a polysubstituted alkylbenzene and/or a polysubstituted alkylnaphthalene. According to the present invention, the aforementioned polysubstituted alkylaromatics can be used in the present invention.
According to one embodiment of the present invention, the polysubstituted alkylbenzene is one or more of para-xylene, ortho-xylene, meta-trimethylbenzene and durene.
According to one embodiment of the present invention, the polysubstituted alkyl naphthalene is a dialkyl naphthalene at an optionally substituted position, preferably one or more of 2, 6-dimethylnaphthalene, 2, 6-diethylnaphthalene and 2, 6-diisopropylnaphthalene.
The invention has no special requirement on the type of the adsorbent, and common molecular sieves, activated carbon and activated alumina can be used in the invention.
According to one embodiment of the invention, the adsorbent is one or more of a molecular sieve, activated carbon, and activated alumina.
According to one embodiment of the invention, the molecular sieve is, for exampleMolecular sieves, ZSM-5 molecular sieves and +.>One or more of the molecular sieves.
According to one embodiment of the invention, the activated carbon is, for example, one or more of powdered activated carbon and granular activated carbon, preferably granular activated carbon.
According to one embodiment of the invention, the adsorbent is used in an amount of 0.1 to 50wt%, preferably 1 to 20wt%, based on the mass of solids in the solid-liquid mixture.
According to one embodiment of the invention, the contacting and separating in the step (2) are performed simultaneously in a device I, wherein the device I comprises a large particle fluidization section I, a small particle fluidization section II and a solid sedimentation section which are communicated from bottom to top, and the solid sedimentation section is positioned at the joint of the large particle fluidization section I and the small particle fluidization section II;
a discharge hole is formed in the bottom of the solid sedimentation section and is used for flowing out the adsorbent, a liquid-solid mixing discharge hole is formed in the small-particle fluidization section II and is used for flowing out polysubstituted carboxyl aromatic hydrocarbon and a liquid phase containing the catalyst, and the liquid phase containing the catalyst after solid-liquid separation is used for oxidization recycling;
the solid-liquid mixture and the adsorbent enter from the bottom of the large-particle fluidization section I and contact with each other, then the organic solvent containing the catalyst and the polysubstituted carboxyl aromatic hydrocarbon flow out from a liquid-solid mixing discharge port of the small-particle fluidization section II, and the adsorbent flows out from a discharge port of the solid sedimentation section. The equipment has the advantages of realizing the recycling of the catalyst and the solid-solid separation at the same time.
According to one embodiment of the invention, the angle α of the connection is <70 °, preferably 30 ° to 60 °.
According to one embodiment of the invention, the bed diameter r1 of the large-particle fluidization section I is 0.1 to 0.8 times, more preferably 0.1 to 0.5 times, the bed diameter r2 of the small-particle fluidization section II.
According to one embodiment of the invention, the bed height H1 of the large-particle fluidization section I is 1.5 to 10 times, more preferably 1.5 to 5 times, the bed height H2 of the small-particle fluidization section II.
According to one embodiment of the invention, the operating temperature of the apparatus I is in the range from 0 to 200 ℃.
According to one embodiment of the invention, the conditions of the contact reaction of step (1) comprise: the mass ratio of the oxidation catalyst, the polysubstituted alkyl aromatic hydrocarbon and the organic solvent is 0.001-1:1:1-100, preferably 0.001-0.2:1:3-10.
According to one embodiment of the invention, the conditions of the contact reaction of step (1) comprise: the temperature is 160-220 ℃, preferably 170-200 ℃.
According to one embodiment of the invention, the conditions of the contact reaction of step (1) comprise: the pressure is 1-10MPa, preferably 2.5-4MPa.
According to one embodiment of the invention, the contacting of step (2) is performed in a batch still and then the separation is performed in a solid-liquid separation device, which is one or more of a filter press device, a centrifuge device, a settling device.
The recovery process of the present invention may be carried out continuously or intermittently.
According to one embodiment of the present invention, the conditions of the step (1) contact reaction may be conventional liquid phase oxidation operating conditions, the invention not being described in detail herein.
According to one embodiment of the invention, the embodiment of the invention is carried out in a device I shown in FIG. 1, comprising: the solid-liquid mixture and the adsorbent enter from the bottom of the large-particle fluidization section I and contact with each other, then the organic solvent containing the catalyst and the polysubstituted carboxyl aromatic hydrocarbon flow out from a liquid-solid mixing discharge port of the small-particle fluidization section II, and the adsorbent flows out from a discharge port of the solid sedimentation section.
In the invention, in the embodiment, r1 is the bed diameter of the large-particle fluidization section I, r2 is the bed diameter of the small-particle fluidization section II, H1 is the bed height of the large-particle fluidization section I, H2 is the bed height of the small-particle fluidization section II, and alpha is the included angle at the large-particle sedimentation section (joint).
Example 1
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), wherein the solvent is acetic acid, and the raw 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 170 ℃ and the pressure is 2.5MPa, and the solid-liquid mixture is obtained after oxidation. After liquid-solid separation, the liquid phase is taken and measured for absorbance at 380nm by a spectrophotometer, converted into corresponding chromaticity (platinum cobalt standard colorimetry) which is 3876, 2g of crude 2,6-NDA is taken and dissolved in 100ml of 0.01mol/L NaOH aqueous solution, the absorbance is measured at 380nm by a spectrophotometer, converted into corresponding chromaticity (platinum cobalt standard colorimetry) which is 2835.
(2) 1kg of oxidized solid-liquid mixture, 10g of granular activated carbon (the dosage of the activated carbon is equal to 10wt% of the mass of 2, 6-NDA) is added, the mixture is mixed and placed in a stirring kettle to be stirred and adsorbed to obtain a mixture, the obtained mixture enters equipment I, and parameters of the equipment I are r1=50 mm, r2=120 mm, H1=1.5 m, H2= 0.5m and alpha=60 degrees; the equipment I is operated at 25 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 125.3.
The obtained liquid phase was measured for Co and Mn contents in the system by ICP at 2125ppm and 2201ppm, respectively, for total bromine in the liquid phase at 5815ppm, and for the liquid phase at 153.2.
Example 2
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 128.1.
The resultant liquid phase was measured for Co and Mn contents of 2188ppm and 2259ppm, respectively, by ICP, for total bromine content of 5933ppm in the liquid phase, and for chromaticity of 159.3 in the liquid phase.
Example 3
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), wherein the solvent is acetic acid, and the crude 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 200 ℃ and the pressure is 4MPa, and a small amount of crude 2,6-NDA is taken for chromaticity analysis to obtain 3112; the color of the liquid phase was 4033.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 200 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 200 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is determined to be 143.3.
The resultant liquid phase was measured for Co and Mn content in the system by ICP, 2154ppm and 2233ppm, respectively, for total bromine content in the liquid phase of 6028ppm, and for chromaticity of the liquid phase of 189.1.
Example 4
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), wherein the solvent is acetic acid, and the crude 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 200 ℃ and the pressure is 4MPa, and a small amount of crude 2,6-NDA is taken for chromaticity analysis to obtain 3112; the color of the liquid phase was 4033.
(2) Cooling the oxidized liquid-solid mixture to 100 ℃, and further mixing the oxidized liquid-solid mixture with granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 100 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 100 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 133.8.
The resulting liquid phase was measured for Co and Mn content in the system by ICP at 2108ppm and 2205ppm, respectively, for total bromine in the liquid phase at 6003ppm, and for chromaticity of the liquid phase at 166.1.
Example 5
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), wherein the solvent is acetic acid, and the crude 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 200 ℃ and the pressure is 4MPa, and a small amount of crude 2,6-NDA is taken for chromaticity analysis to obtain 3112; the color of the liquid phase was 4033.
(2) Cooling the oxidized liquid-solid mixture to 20 ℃, and further mixing the oxidized liquid-solid mixture with granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 20 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the operating temperature of the equipment I is 20 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 146.7.
The resultant liquid phase was measured for Co and Mn contents in the system by ICP at 2038ppm and 2066ppm, respectively, for total bromine in the liquid phase at 5903ppm, and for chromaticity of the liquid phase at 169.8.
Example 6
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent is formic acid, the crude 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 170 ℃ and the pressure is 3MPa, and a small amount of crude 2,6-NDA is taken for chromaticity analysis, which is 3452; the color of the liquid phase was 4256.
(2) Cooling the oxidized liquid-solid mixture to 20 ℃, and further mixing the oxidized liquid-solid mixture with granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 20 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the operating temperature of the equipment I is 20 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is 177.5.
The resultant liquid phase was measured for Co and Mn content in the system by ICP at 2034ppm and 2054ppm, respectively, for total bromine content in the liquid phase at 5946ppm, and for chromaticity of the liquid phase at 192.7.
Example 7
(1) The catalyst comprises the following components in percentage by mass: 2, 6-dimethylnaphthalene: solvent = 0.06:15:100, catalyst molar ratio Co: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), wherein the solvent is acetic acid, and the raw 2,6-NDA is prepared by oxidation reaction under the conditions that the reaction temperature is 170 ℃ and the pressure is 3MPa, and a small amount of raw 2,6-NDA is taken for chromaticity analysis, so that 2854 is obtained; the color of the liquid phase was 3168.
(2) Cooling the oxidized liquid-solid mixture and preparing the granular activated carbon into coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 108.8.
The resulting liquid phase was measured for Co and Mn content in the system by ICP, 134ppm and 136ppm, respectively, for total bromine in the liquid phase, 389ppm, and for chromaticity of the liquid phase, 122.5.
Example 8
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:2 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 118.3.
The resulting liquid phase was measured for Co and Mn content in the system by ICP, 2137ppm and 2242ppm, respectively, for total bromine in the liquid phase, 5918ppm, and for chromaticity of the liquid phase, 157.6.
Example 9
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and activated carbon according to the following crude 2,6-NDA: the ratio of activated carbon=10:3 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 117.8.
The resulting liquid phase was measured for Co and Mn content in the system by ICP, 2132ppm and 2228ppm, respectively, for total bromine in the liquid phase, 5895ppm, and for chromaticity of the liquid phase, 156.9.
Example 10
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:0.1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 244.6.
The resulting liquid phase was measured for Co and Mn content in the system by ICP, 2177ppm and 2210ppm, respectively, for total bromine in the liquid phase, 5994ppm, and for chromaticity of the liquid phase, 196.7.
Example 11
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=20 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 128.3. The obtained liquid phase was measured for Co and Mn contents in the system by ICP, 2183ppm and 2256ppm, respectively, and the total bromine content in the liquid phase was 5938ppm, and the chromaticity of the liquid phase was 139.8. However, when discharging the large granule sedimentation section, bridging phenomenon is easy to occur at the discharge port, and the adsorbent granules can not be smoothly discharged.
Example 12
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=30 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is measured to be 127.5. The obtained liquid phase was measured for Co and Mn contents in the system by ICP, 2179ppm and 2258ppm, respectively, and the total bromine content in the liquid phase was 5956ppm, and the color of the liquid phase was 138.3. When the large-particle sedimentation section is used for discharging, the discharge hole is smooth in discharging.
Example 13
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=50 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=45 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is determined to be 127.7. The obtained liquid phase was measured for Co and Mn contents in the system by ICP, 2188ppm and 2271ppm, respectively, and the total bromine content in the liquid phase was 5962ppm, and the chromaticity of the liquid phase was 139.0. When the large-particle sedimentation section is used for discharging, the discharge hole is smooth in discharging.
Example 14
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3 (cobalt acetate, manganese acetate and potassium bromide), the solvent was acetic acid, and the crude 2,6-NDA was prepared by oxidation at a reaction temperature of 170℃and a pressure of 2.5MPa, the crude 2,6-NDA obtained in example 1 having a color of 2835 and the liquid phase having a color of 3876.
(2) Mixing the oxidized liquid-solid mixture and granular activated carbon according to the coarse 2,6-NDA: the ratio of activated carbon=10:1 goes directly into the plant 1 at 170 ℃, the parameters of the plant i involved being r1=96 mm, r2=120 mm, h1=1.5 m, h2=0.5 m, α=60 °; the equipment I is operated at 170 ℃, the mixture extracted from the tower top is collected and filtered, the obtained solid phase is dried, and the chromaticity is determined to be 119.8. The obtained liquid phase was measured for Co and Mn contents in the system by ICP, 2187ppm and 2249ppm, respectively, and the total bromine content in the liquid phase was 5949ppm, and the chromaticity of the liquid phase was 138.1. However, the 2,6-NDA obtained by filtering the mixture taken from the top of the column contains incompletely separated granular activated carbon particles.
Comparative example 1
(1) The catalyst comprises the following components in percentage by mass: 2, 6-diisopropylnaphthalene: solvent=1:15:100, molar ratio Co of the elements of the catalyst: mn: br=1:1:3, the solvent is acetic acid, and the crude 2,6-NDA is prepared by oxidation reaction at a reaction temperature of 170 ℃ and a pressure of 2.5MPa, and the chromaticity of the crude 2,6-NDA obtained in example 1 is 2835.
(2) Filtering and separating the liquid-solid mixture in the step (1) to obtain a catalyst-containing acetic acid solution, and adding 5g of active carbon into each 100g of solution to decolorize the solution to obtain a clear red catalyst-containing acetic acid recovery solution; filtering and separating to obtain crude 2,6-NDA, adding azodicarbonamide for dissolving (the dissolving temperature is 50 ℃, 6g of crude 2,6-NDA can be dissolved in 100g of solvent), and obtaining crude 2,6-NDA according to the 2,6-NDA: the decolorization was performed for 1h at an active carbon=10:1 ratio, and a small sample was taken to evaporate the solvent and tested for the color value of 2,6-NDA after decolorization, which was 253.2 in color.
According to the embodiment of the invention, the catalyst content in the solvent after treatment is equivalent to that before oxidation reaction by adopting the catalyst recycling method, and the chromaticity of the solvent is lower; thus, the catalyst solvent is recycled, and the crude 2,6-NDA is decolorized, so that compared with the prior scheme (comparative example 1), the process is greatly simplified, and the decolorizing effect is improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (20)
1. A method for recovering a liquid phase oxidation catalyst, comprising:
(1) The polysubstituted alkyl arene is contacted and reacted with an oxidation catalyst in an organic solvent to obtain a solid-liquid mixture;
(2) Contacting the solid-liquid mixture with an adsorbent, and separating to obtain a liquid phase containing an organic solvent and a catalyst, the adsorbent and a reactant polysubstituted carboxyl aromatic hydrocarbon, wherein the oxidation catalyst contains metal and halogen atoms; the contact and separation in the step (2) are carried out simultaneously in a device I, wherein the device I comprises a large particle fluidization section I, a small particle fluidization section II and a solid sedimentation section which are communicated from bottom to top, and the solid sedimentation section is positioned at the joint of the large particle fluidization section I and the small particle fluidization section II;
a discharge hole is formed in the bottom of the solid sedimentation section and is used for flowing out the adsorbent, a liquid-solid mixing discharge hole is formed in the small-particle fluidization section II and is used for flowing out polysubstituted carboxyl aromatic hydrocarbon and a liquid phase containing the catalyst, and the liquid phase containing the catalyst after solid-liquid separation is used for oxidization recycling;
the solid-liquid mixture and the adsorbent enter from the bottom of the large-particle fluidization section I and contact with each other, then the organic solvent containing the catalyst and the polysubstituted carboxyl aromatic hydrocarbon flow out from a liquid-solid mixing discharge port of the small-particle fluidization section II, and the adsorbent flows out from a discharge port of the solid sedimentation section.
2. The recycling method according to claim 1, wherein the method comprises: and (3) recycling the liquid phase containing the organic solvent and the catalyst as a reaction material in the step (1).
3. The recycling method according to claim 1, wherein the angle of the junction is <70 °.
4. A recycling method according to claim 3, wherein the angle α of the junction is 30 ° to 60 °.
5. The recovery method according to claim 1, wherein the bed diameter of the large particle fluidization section i is 0.1 to 0.8 times the bed diameter of the small particle fluidization section ii.
6. The recovery method according to claim 5, wherein the bed diameter of the large particle fluidization section I is 0.1 to 0.5 times the bed diameter of the small particle fluidization section II.
7. The recovery method according to claim 4, wherein the bed diameter of the large particle fluidization section I is 0.1 to 0.8 times the bed diameter of the small particle fluidization section II.
8. The recovery method according to claim 7, wherein the bed diameter of the large particle fluidization section I is 0.1 to 0.5 times the bed diameter of the small particle fluidization section II.
9. The recovery process of claim 1 wherein the bed height of the large particle fluidization section i is 1.5 to 10 times the bed height of the small particle fluidization section ii.
10. The recovery process of claim 9 wherein the bed height of the large particle fluidization section i is 1.5 to 5 times the bed height of the small particle fluidization section ii.
11. A recovery process according to claim 3, wherein the bed height of the large particle fluidization section i is 1.5 to 10 times the bed height of the small particle fluidization section ii.
12. The recovery process of claim 11 wherein the bed height of the large particle fluidization section i is 1.5 to 5 times the bed height of the small particle fluidization section ii.
13. The recovery process of claim 4 wherein the bed height of the large particle fluidization section I is 1.5 to 10 times the bed height of the small particle fluidization section II.
14. The recovery process of claim 13 wherein the bed height of the large particle fluidization section i is 1.5 to 5 times the bed height of the small particle fluidization section ii.
15. The recovery method according to any one of claims 1 to 14, wherein the operating temperature of the apparatus i is 0 to 200 ℃.
16. The recycling method according to any one of claims 1 to 14, wherein,
the metal of the oxidation catalyst is Co and/or Mn, and the halogen atom is Br; and/or
The organic solvent is one or more of aliphatic carboxylic acids; and/or
The polysubstituted alkyl aromatic hydrocarbon is polysubstituted alkylbenzene and/or polysubstituted alkyl naphthalene; the polysubstituted alkylbenzene is one or more of paraxylene, o-xylene, m-xylene, meta-trimethylbenzene and durene, and the polysubstituted alkyl naphthalene is dialkyl naphthalene at any substitution position; and/or
The adsorbent is one or more of molecular sieve, activated carbon and activated alumina.
17. The recycling method according to any one of claims 1 to 14, wherein,
the organic solvent is C1-C6 carboxylic acid; and/or
The polysubstituted alkyl naphthalene is one or more of 2, 6-dimethylnaphthalene, 2, 6-diethylnaphthalene and 2, 6-diisopropylnaphthalene; and/or
The adsorbent is activated carbon.
18. The recycling method according to claim 17, wherein,
the organic solvent is acetic acid; and/or
The adsorbent is granular activated carbon.
19. The recycling method according to any one of claims 1 to 14, wherein,
the dosage of the adsorbent is 0.1-50wt% of the solid mass in the solid-liquid mixture; and/or
The total content of the oxidation catalyst in the organic solvent is not more than 20wt%;
the conditions for the contacting reaction of step (1) include:
the mass ratio of the oxidation catalyst to the polysubstituted alkyl aromatic hydrocarbon to the organic solvent is 0.001-1:1:1-100; the temperature is 160-220 ℃ and the pressure is 1-10MPa.
20. The recycling method according to claim 19, wherein,
the dosage of the adsorbent is 1-20wt% of the solid mass in the solid-liquid mixture; and/or
The conditions for the contacting reaction of step (1) include:
the mass ratio of the oxidation catalyst to the polysubstituted alkyl aromatic hydrocarbon to the organic solvent is 0.001-0.2:1:3-10; the temperature is 170-200deg.C, and the pressure is 2.5-4MPa.
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| CN1359313A (en) * | 1999-08-17 | 2002-07-17 | 流动程序技术公司 | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid |
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| CN102309992A (en) * | 2010-06-30 | 2012-01-11 | 中国石油化工股份有限公司 | Method for recovering cobalt-manganese catalyst in para-dimethylbenzene oxidation mother liquor |
| CN105688990A (en) * | 2016-01-22 | 2016-06-22 | 福建洋屿环保科技股份有限公司 | Method for regenerating cobalt and manganese acetate compound catalyst from PTA (Pure Terephthalic Acid) oxidization residues |
| CN107586973A (en) * | 2017-07-18 | 2018-01-16 | 百川化工(如皋)有限公司 | A kind of method of Call Provision manganese in waste material from cobalt-manganese catalyst |
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| CN1359313A (en) * | 1999-08-17 | 2002-07-17 | 流动程序技术公司 | Recovery process for oxidation catalyst in the manufacture of aromatic carboxylic acid |
| CN1861570A (en) * | 2006-06-19 | 2006-11-15 | 常州市佳森化工有限公司 | Tech. of preparing amino benz methyl-phenoxide by nitro methyl-phenoxide mixture catalyzing hydrogenation |
| CN102309992A (en) * | 2010-06-30 | 2012-01-11 | 中国石油化工股份有限公司 | Method for recovering cobalt-manganese catalyst in para-dimethylbenzene oxidation mother liquor |
| CN105688990A (en) * | 2016-01-22 | 2016-06-22 | 福建洋屿环保科技股份有限公司 | Method for regenerating cobalt and manganese acetate compound catalyst from PTA (Pure Terephthalic Acid) oxidization residues |
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