CN115028545A - Preparation method of phenol extracting agent DW503 in wastewater - Google Patents
Preparation method of phenol extracting agent DW503 in wastewater Download PDFInfo
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- CN115028545A CN115028545A CN202210597572.7A CN202210597572A CN115028545A CN 115028545 A CN115028545 A CN 115028545A CN 202210597572 A CN202210597572 A CN 202210597572A CN 115028545 A CN115028545 A CN 115028545A
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- acetic acid
- acid
- diisooctylamine
- phenol
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229960000583 acetic acid Drugs 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 238000007112 amidation reaction Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000005086 pumping Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
- 238000005070 sampling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- KMGFVPGVMMBATJ-UHFFFAOYSA-N n,n-bis(2-ethylhexyl)acetamide Chemical compound CCCCC(CC)CN(C(C)=O)CC(CC)CCCC KMGFVPGVMMBATJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013405 beer Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 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 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 15
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 230000009435 amidation Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WFHJRRVARWWPDH-UHFFFAOYSA-N n-octan-2-yloctan-2-amine Chemical compound CCCCCCC(C)NC(C)CCCCCC WFHJRRVARWWPDH-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RTTCFFTVCUNXLX-UHFFFAOYSA-N n,n-di(octan-2-yl)acetamide Chemical compound CCCCCCC(C)N(C(C)=O)C(C)CCCCCC RTTCFFTVCUNXLX-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a phenol high-efficiency extracting agent DW503 in wastewater, which comprises the following steps: 1) putting diisooctylamine and a supported acid catalyst into an amidation reaction kettle, replacing with nitrogen, and filling nitrogen to about 0.1 MPa; 2) starting stirring, heating to 180-240 ℃, slowly pumping glacial acetic acid into the reactor for reaction, and feeding generated water into an oil-water separator through a condenser; 3) after the pumping is finished, carrying out heat preservation reaction, and sampling until the content of the diisooctylamine is less than 0.5 percent, otherwise, adding glacial acetic acid in a proper amount; 4) returning the generated water in the oil-water separator to the next batch for reaction; 5) pressing the qualified materials in the amidation reaction kettle into a rectifying kettle, and rectifying to obtain an extractant DW503 finished product, wherein the product content is more than 98 percent, and the yield is more than 96 percent; the extracting agent obtained by the invention is used for the extraction experiment of the waste water phenol, the dephenolization rate of the waste water can reach more than 99.99 percent, the extracting agent is very efficient and stable in property, and the extracting agent can be repeatedly used.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of an extracting agent N, N-di (2-ethylhexyl) acetamide (DW503) capable of efficiently recovering phenol in wastewater.
Background
Phenol is a basic chemical raw material and is used for industrial production in large quantity, so phenol-containing waste water is relatively common and relatively large in quantity, and is one of the relatively serious harmful industrial waste water. At present, the treatment of phenol-containing waste water at home and abroad generally adopts a biochemical method for low-concentration phenol-containing waste water and adopts a solvent extraction method for high-concentration phenol-containing waste water. According to the basic principle of complex extraction, the developed novel high-efficiency complex type extracting agent has wide market. It can be widely used for treating and recycling phenol-containing wastewater in the industries of pesticide, chemical industry, pharmacy, coking, dye, paint, plastics and the like.
The N503 extractant, namely N, N-di (1-methylheptyl) acetamide, is used at present on the market, although the dephenolization efficiency of the product is high, the product is synthesized by basically adopting di-sec-octylamine to react with acetic anhydride, the price of the di-sec-octylamine is high, the di-sec-octylamine is difficult to obtain, the acetic anhydride also has the problem of high price, and the product belongs to easily-made toxins, and the purchase procedure is complicated.
Therefore, the research of an extracting agent with simple preparation method, low cost and good extraction effect becomes one of the research focuses in the field at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of an extracting agent DW503 for efficiently recovering phenol in wastewater, wherein the extracting agent DW503 is N, N-di (2-ethylhexyl) acetamide, acetic acid is used as a reaction raw material to replace acetic anhydride, and the extracting agent DW503 reacts with secondary amine with a long carbon chain, so that a novel supported acid catalyst is researched to ensure high conversion rate, high yield and high purity of DW503, the purpose can be achieved, the extracting agent has high-efficiency extraction performance on phenol in wastewater, and the removal rate of phenol reaches more than 99.99%.
The invention discloses a preparation method of a phenol extracting agent DW503 in wastewater, which comprises the following steps:
1) preparing 10-50% aqueous solution of acid, adding the aqueous solution into a carrier, stirring and aging at room temperature, settling, removing an upper water layer, and drying a lower paste to obtain a catalyst for later use, wherein the drying temperature is 105 ℃, and the drying is carried out until the volatile content is less than 0.5% and qualified;
2) adding diisooctylamine and the catalyst prepared in the step 1) into an amidation reaction kettle, replacing with nitrogen, and then filling nitrogen until the pressure is 0.08-0.15 MPa;
3) stirring and heating to 180-240 ℃, slowly pumping glacial acetic acid to the bottom of the kettle, reacting diisooctylamine with glacial acetic acid, and separating generated water vapor from the top of the kettle to a condenser;
4) after the glacial acetic acid pump is finished, carrying out heat preservation reaction, sampling and tracking until the content of the diisooctylamine is less than 0.5 percent, and finishing the reaction;
5) pressing the reaction liquid obtained in the step 4) into a rectifying still for rectification to obtain a phenol extracting agent DW503 finished product, namely N, N-di (2-ethylhexyl) acetamide, wherein the product rectification condition is negative pressure (2-3mmHg) rectification, collecting fractions with the top temperature of 150-,
the reaction equation of the present invention is as follows:
further, the invention defines that the acid in the step 1) is one or a mixture of two of phosphoric acid, phosphorous acid, acetic acid, hypophosphorous acid or sulfuric acid; the concentration of the aqueous solution prepared from the acid is 15-30%; the carrier is SiO 2 、γ-Al 2 O 3 One or a mixture of more of carclazyte, beer silica gel or 13x molecular sieve raw powder, and the specific surface area of the carrier is 300-800 m 2 The mass ratio of the acid to the carrier is 0.1-0.3: 1.
Further, the invention also defines the feeding molar ratio of the diisooctylamine to the glacial acetic acid in the step 2) to be 1: 1.1-1.8, preferably 1: 1.1-1.3; the feeding mass ratio of the diisooctylamine to the supported acid catalyst is 1: 0.015-0.03. .
Further, the invention also limits the pumping speed of the glacial acetic acid in the step 3) to be 100-200 kg/h, and mainly controls the temperature of the top of the amidation reaction kettle to be 140-170 ℃; the liquid distributor is arranged at the bottom of the amidation reaction kettle, and glacial acetic acid is pumped into the liquid distributor at the bottom of the amidation reaction kettle; and because the reaction temperature is higher than the boiling point of acetic acid, glacial acetic acid is selected to be pumped into the bottom of the reaction kettle, and the acetic acid can be reacted more completely under the action of the liquid distributor.
Further, the invention also defines that the distillation conditions in the step 5) are negative pressure distillation (2-3mmHg in the embodiment of the invention), and fractions with the top temperature of 150 ℃ and 170 ℃ are collected.
Furthermore, the invention also limits the water layer separated by the oil-water separator in the step 3) to be used as the raw material of the next batch, the raw material is added into an amidation reaction kettle containing diisooctylamine and a catalyst, after nitrogen gas replacement, the temperature is raised to 150 ℃ for reaction, the acetic acid in the water layer is completely reacted, the generated water enters the oil-water separator for separation, the obtained water layer is basically water and can be directly discarded, and the separated oil layer can be returned to the reaction kettle for mixing.
Furthermore, the invention also defines that in the step 4), when sampling and tracking are carried out, if the content of the raw material diisooctylamine is more than 0.5%, glacial acetic acid is supplemented for reaction, the reaction is ended until the content of the raw material diisooctylamine is less than 0.5%, and the heat preservation time is generally 3-5 hours.
Further, the rectification residue in the step 5) is used as a catalyst and added into the next batch for reuse.
The invention adopts diisooctylamine and acetic acid as raw materials, the diisooctylamine is a product disclosed by the applicant, and the acetic acid is easier to purchase than acetic anhydride, the obtained phenol extractant DW503, namely N, N-bis (2-ethylhexyl) acetamide, has the product content of more than 98 percent, and the yield of more than 96 percent; the dephenolizing efficiency is high, the dephenolizing rate of the wastewater can reach more than 99.99 percent, the concentration of phenol in the treated wastewater can reach the national industrial wastewater discharge standard (less than or equal to 0.5ppm), and the method has the characteristics of low operation cost, small solvent loss and recoverable phenols; the product is especially suitable for treating high-concentration phenol-containing wastewater with low acidity (PH <4) and low temperature (20 ℃), and the dephenolizing extraction rate can reach more than 99.99 percent.
Detailed Description
EXAMPLE 1 preparation of phenol extractant DW503(N, N-bis (2-ethylhexyl) acetamide)
1) Preparing a catalyst: the commercially available 375kgSiO 2 Powder and 125kg of gamma-Al 2 O 3 Powder (both having a specific surface area of 500m 2 Mixing uniformly, adding deionized water, cleaning, removing impurities, removing upper-layer water, adding 300kg (16.67%) of phosphorous acid aqueous solution, stirring at room temperature overnight, standing to remove upper-layer water, and drying lower-layer paste at 105 ℃ to obtain a catalyst for later use;
2) synthesizing: adding 5000kg of diisooctylamine (99%) and 100kg of the catalyst prepared in the step 1) into an amidation reaction kettle, after nitrogen replacement, filling nitrogen to 0.1MPa, starting stirring, heating to 180-190 ℃, starting an automatic circulating water regulating valve of a condenser, starting to pump 2200kg of glacial acetic acid at a pumping speed of 150kg/h, maintaining the top temperature of the amidation kettle at 140-170 ℃, after about 15h, finishing the pump, preserving the heat for 5h, sampling and carrying out GC detection, wherein the weight ratio of diisooctylamine: 0.4 percent of DW503, 97.5 percent of DW, and the reaction is finished; 490kg of glacial acetic acid aqueous solution (the water content is 76%, and the rest is unreacted glacial acetic acid) is obtained from the water layer in the oil-water separator and is used as a raw material to be put into the next batch for reaction; and (3) after the reaction is finished, feeding the crude product (containing the catalyst) into a rectifying still, carrying out negative pressure rectification under 2-3mmHg, cutting off a small amount of front distillate, collecting the distillate at the temperature of 150-170 ℃ to obtain 5682kg of finished product, wherein the content is 98.5%, the yield is 96.8%, and the rectification residue is mainly used as the catalyst and collected for reuse.
Example 2: preparation method of phenol extracting agent DW503(N, N-di (2-ethylhexyl) acetamide)
1) Preparing a catalyst: 375kg of commercially available beer silica gel powder (surface area 380 m) 2 /g) surface area and 125kg of gamma-Al 2 O 3 Powder (specific surface area 500 m) 2 Mixing uniformly, adding deionized water for cleaning, removing impurities, removing upper-layer water, adding 300kg (25%) of phosphorous acid aqueous solution, stirring at room temperature overnight, standing to remove upper-layer water, and drying lower-layer paste at 105 ℃ to obtain a catalyst for later use;
2) synthesizing: putting 5000kg of diisooctylamine (99%) and 80kg of catalyst prepared in the step 1) into an amidation reaction kettle, after nitrogen replacement, filling nitrogen to 0.1MPa, starting stirring, heating to 200-210 ℃, keeping the temperature for 1h, starting an automatic regulating valve for circulating water of a condenser, starting pumping 1614kg of glacial acetic acid, wherein the pumping speed is 150kg/h, keeping the top temperature of the amidation kettle at 140-170 ℃, after about 11h, pumping, keeping the temperature for 5h, sampling and carrying out GC detection, wherein the diisooctylamine: 0.38 percent of the total weight, DW503:97.1 percent, and the reaction is ended; 740kg of glacial acetic acid aqueous solution (water content: 50%, the rest is unreacted glacial acetic acid) is obtained from the water layer in the oil-water separator; and (3) feeding the crude product (containing the catalyst) obtained by the reaction into a rectifying still, carrying out negative pressure rectification under 2-3mmHg, cutting off a small amount of front distillate, collecting the distillate at the temperature of 150-170 ℃ to obtain 5635kg of finished product, wherein the content is 98.3%, the yield is 96%, and collecting the rectification residue for later use.
Example 2-1: application of catalyst and acetic acid
5000kg of diisooctylamine (99%), 740kg of the liquid in the oil-water separator of example 2 and the residue of the rectifying still of example 2 were put into an amidation reaction kettle, nitrogen was charged to 0.1MPa after nitrogen substitution, the temperature was raised to 150 ℃ to carry out a reaction, the produced water was received through the oil-water separator to obtain 380kg of water (substantially pure water), which was discarded; and then starting stirring, raising the temperature to 220-240 ℃, keeping the temperature for 1h, starting an automatic circulating water regulating valve of a condenser, starting to pump 1244kg of new glacial acetic acid at a pumping speed of 150kg/h, maintaining the top temperature of the amidation kettle at 140-170 ℃, completing pumping after about 8h, keeping the temperature for 5h, sampling and performing GC detection, wherein the mass ratio of diisooctylamine: 0.45 percent and DW503:97.0 percent. The water layer in the oil-water separator was separated to obtain 550kg (water content: 70%, remainder unreacted glacial acetic acid) of glacial acetic acid aqueous solution; and (3) feeding the crude product (containing the catalyst) obtained by the reaction into a rectifying still, rectifying under negative pressure of 2-3mmHg, cutting off a small amount of front distillate, and collecting the distillate at the temperature of 150-170 ℃ to obtain 5692kg of finished product with the content of 98.3% and the yield of 97%.
Example 3: preparation method of phenol extracting agent DW503(N, N-di (2-ethylhexyl) acetamide)
1) Preparing a catalyst: 500kg of a commercially available 13X molecular sieve raw powder (specific surface area 280 m) 2 /g) mixing, adding deionized water, cleaning, removing impurities, removing upper water, adding 500kg (20%) phosphorous acid aqueous solution, stirring at room temperatureStirring overnight, standing to remove the water on the upper layer, and drying the lower layer at 105 ℃ to obtain a catalyst for later use;
2) synthesizing: adding 5000kg of diisooctylamine (99%) and 120kg of a catalyst prepared in the step 1) into an amidation reaction kettle, adding nitrogen to 0.1MPa after nitrogen replacement, starting stirring, heating to 230-240 ℃, keeping the temperature for 1h, starting an automatic circulating water regulating valve of a condenser, starting to pump 1480kg of glacial acetic acid, wherein the pumping speed is 150kg/h, the top temperature of the amidation kettle is maintained at 140-170 ℃, after about 10h, the pump is finished, keeping the temperature for 5h, sampling and detecting by GC, wherein the weight ratio of diisooctylamine: 0.46 percent and DW503:96.6 percent. 540kg (moisture: 67%, remainder unreacted glacial acetic acid) of an aqueous glacial acetic acid solution in the oil-water separator was put into the next batch; and (3) feeding the crude product (containing the catalyst) obtained by the reaction into a rectifying still, carrying out negative pressure rectification under 2-3mmHg, cutting off a small amount of front distillate, and collecting the distillate at the temperature of 150-170 ℃ to obtain 5660kg of finished product with the content of 98.1% and the yield of 96.4%.
Examples 4 to 8
The invention discovers that the synthesis of products is facilitated, the conversion rate is improved and the reaction time is shortened under the action of a supported acid catalyst through a large amount of experiments and researches because diisooctylamine has larger steric hindrance and is difficult to directly form amide with acid, and compared with an embodiment without a catalyst, the catalyst and the reaction conditions prepared in the embodiment 1 are adopted in the invention, and the results are shown in the experimental data shown in the table 1:
TABLE 1 comparison of experimental data
As can be seen from Table 1, the reaction rate and conversion rate of diisooctylamine and acetic acid are greatly improved under the action of the supported acid catalyst.
Application test:
1. taking phenol-containing wastewater (pH is 3.4, phenol concentration is 10000ppm) from a production workshop of Wanshengmen Limited company in Zhejiang, adopting a three-stage continuous extraction device of the company, and respectively taking an extracting agent DW503, an externally purchased extracting agent N503 and recovered DW503 obtained by the invention as extracting agents; measuring indexes such as phenol content in water, water in the extracting agent, recovery rate of the extracting agent and the like after liquid separation;
2. the water used in the first-stage extraction is phenol-containing wastewater, and the effluent after the first-stage extraction is used in the second-stage extraction; the third-stage extraction uses the effluent after the second-stage extraction, and the extractants used in the first-stage extraction, the second-stage extraction and the third-stage extraction are extractants with the same specification;
3. in order to verify the heat resistance and recovery rate of the extractant, the extractant was distilled under about 500Pa, and the recovery of fractions and the reuse of the recovered extractant were observed, as shown in table 2.
TABLE 2 comparison of the application data of the present invention with those of the commercial products
As can be seen from Table 2, DW503 of the present invention is a highly efficient phenol extractant. The invention adopts the self-made negative acid catalyst, solves the problems of low conversion rate and slow reaction rate of acetic acid and diisooctylamine, replaces acetic anhydride with acetic acid, has lower cost and easier acquisition of raw materials, and simultaneously obtains high-content DW 503. The DW503 phenol removal rate can reach 99.99 percent, is 98.7 percent higher than the commercial N503 phenol removal rate, and can reach the national phenol-containing wastewater discharge standard (less than or equal to 0.5ppm) through three-stage extraction.
Claims (10)
1. A preparation method of a phenol extracting agent DW503 in wastewater is characterized by comprising the following steps:
1) preparing 10-50% aqueous solution of acid, adding the aqueous solution into a carrier, stirring at room temperature, aging, settling, removing an upper water layer, and drying a lower paste to obtain a supported acid catalyst for later use;
2) adding diisooctylamine and the supported acid catalyst prepared in the step 1) into an amidation reaction kettle, replacing with nitrogen, and then filling nitrogen until the pressure is 0.08-0.15 MPa;
3) stirring and heating to 180-240 ℃, slowly pumping glacial acetic acid to the bottom of the kettle, reacting diisooctylamine with glacial acetic acid, condensing generated water vapor from the top of the kettle to a condenser, and separating in an oil-water separator;
4) after the glacial acetic acid pump is finished, carrying out heat preservation reaction, sampling and tracking until the content of the diisooctylamine is less than 0.5 percent, and finishing the reaction;
5) pressing the reaction liquid obtained in the step 4) into a rectifying still for rectification to obtain a finished product of the phenol extracting agent DW503, namely N, N-di (2-ethylhexyl) acetamide.
2. The method for preparing the phenol extractant DW503 in the wastewater according to claim 1, characterized in that the acid in the step 1) is one or a mixture of two of phosphoric acid, phosphorous acid, acetic acid, hypophosphorous acid or sulfuric acid; the concentration of the aqueous solution prepared from the acid is 15-30%.
3. The method for preparing phenol extractant DW503 in wastewater according to claim 1, characterized in that the carrier in step 1) is SiO 2 、γ-Al 2 O 3 One or a mixture of more of carclazyte, beer silica gel or 13x molecular sieve raw powder, and the specific surface area of the carrier is 300-800 m 2 /g。
4. The method for preparing the phenol extracting agent DW503 in the wastewater according to claim 1, characterized in that the mass ratio of the acid to the carrier in the step 1) is 0.1-0.3: 1.
5. The method for preparing the phenol extracting agent DW503 in the wastewater according to claim 1, characterized in that the feeding molar ratio of diisooctylamine and glacial acetic acid in the step 2) is 1: 1.1-1.8, preferably 1: 1.1-1.3; the feeding mass ratio of the diisooctylamine to the supported acid catalyst is 1: 0.015-0.03.
6. The method for preparing the phenol extractant DW503 in the wastewater according to claim 1, characterized in that the glacial acetic acid pumping speed in the step 3) is 100-200 kg/h, the kettle bottom of the amidation reaction kettle is provided with a liquid distributor, and the glacial acetic acid is pumped into the liquid distributor at the kettle bottom and is further dispersed by the liquid distributor.
7. The method for preparing the phenol extractant DW503 in the wastewater as claimed in claim 1, characterized in that the rectification in the step 5) is negative pressure rectification and the fraction with the top temperature of 150-170 ℃ is collected.
8. The process according to any one of claims 1 to 7, wherein the aqueous layer separated from the oil-water separator in step 3) is used as a raw material for the next batch, and the aqueous layer is introduced into an amidation reaction vessel containing diisooctylamine and a supported acid catalyst, and after nitrogen substitution, the temperature is raised to 150 ℃ to carry out the reaction, acetic acid in the aqueous layer is reacted completely, and the produced water is separated in the oil-water separator and the aqueous layer is discarded.
9. The method for preparing the phenol extractant DW503 in the wastewater according to any of claims 1 to 7, characterized in that in the step 4), when the sampling and tracking are carried out, if the diisooctylamine as the raw material is not reacted, glacial acetic acid is supplemented to carry out the reaction until the content of the diisooctylamine as the raw material is less than 0.5 percent, and the reaction is ended.
10. The method for preparing the phenol extractant DW503 in the wastewater according to any of claims 1-7, characterized in that the rectification residue in the step 5) is added as a catalyst for the next batch for reuse.
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