CN114195822B - Method for recycling triphenyl phosphate in 7-ACCA waste liquid - Google Patents
Method for recycling triphenyl phosphate in 7-ACCA waste liquid Download PDFInfo
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- CN114195822B CN114195822B CN202111478261.0A CN202111478261A CN114195822B CN 114195822 B CN114195822 B CN 114195822B CN 202111478261 A CN202111478261 A CN 202111478261A CN 114195822 B CN114195822 B CN 114195822B
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 238000005406 washing Methods 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000004042 decolorization Methods 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 230000032798 delamination Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000007670 refining Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000012776 electronic material Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000012450 pharmaceutical intermediate Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- QYIYFLOTGYLRGG-GPCCPHFNSA-N cefaclor Chemical compound C1([C@H](C(=O)N[C@@H]2C(N3C(=C(Cl)CS[C@@H]32)C(O)=O)=O)N)=CC=CC=C1 QYIYFLOTGYLRGG-GPCCPHFNSA-N 0.000 description 2
- 229960005361 cefaclor Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- OMSBSIXAZZRIRW-UHFFFAOYSA-N 2-methylpyridine;hydrochloride Chemical compound Cl.CC1=CC=CC=N1 OMSBSIXAZZRIRW-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention provides a method for recycling triphenyl phosphate in 7-ACCA waste liquid, which comprises the following steps: adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing a lower water phase solution, and retaining an upper oil phase solution to obtain a washing solution; regulating the pH value of the washing solution by using a regulator to ensure that the pH value of the washing solution is more than or equal to 7, and concentrating under reduced pressure until no fraction is produced; adding an alkane solvent into the concentrated solution, standing for layering after uniformly mixing, reserving an upper layer solution, adding the alkane solvent again into a lower layer solution for repeated extraction, and combining and mixing the obtained upper layer solution; crystallizing and drying the extraction solution to obtain the triphenyl phosphate. The method for recycling the triphenyl phosphate in the 7-ACCA waste liquid has simple process, can obtain high-quality triphenyl phosphate without repeated refining, and has high recovery rate and lower recovery cost.
Description
Technical Field
The invention belongs to the technical field of byproduct recovery, and particularly relates to a method for recovering triphenyl phosphate in 7-ACCA waste liquid.
Background
7-ACCA, chemical name 7-amino-3-chloro-3-cefaclor-4-carboxylic acid, is an important intermediate in the synthesis process of cefaclor. Waste liquid is generated in the process of synthesizing the 7-ACCA, and a large amount of triphenyl phosphate byproducts are contained in the waste liquid, if the byproducts cannot be recovered, a large amount of phosphorus-containing solid waste is caused, the harmless treatment difficulty is high, and the resource waste is caused.
Triphenyl phosphate is an important chemical intermediate, and is widely applied to the fields of flame retardant materials, electronic materials, pharmaceutical intermediates, plasticizing materials and the like. At present, the triphenyl phosphate is recovered to have the problems of low purity and color difference, the requirements of electronic materials and medical intermediates are difficult to meet, repeated refining is needed to meet the requirements, and further the triphenyl phosphate is lower in recovery rate and higher in recovery cost.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a high-efficiency and low-cost recovery method, which can recover high-quality triphenyl phosphate from 7-ACCA waste liquid, and the recovered triphenyl phosphate has high purity and good color, and can meet the requirements of flame retardant materials and/or electronic materials and pharmaceutical intermediates.
The invention provides a method for recycling triphenyl phosphate in 7-ACCA waste liquid, which comprises the following steps:
S1, adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing a lower water phase solution, and retaining an upper oil phase solution to obtain a washing solution;
S2, regulating the pH value of the washing solution by using a regulator to ensure that the pH value of the washing solution is more than or equal to 7, and concentrating under reduced pressure until no fraction is produced to obtain a concentrated solution;
s3, adding an alkane solvent into the concentrated solution, keeping the temperature at 30-75 ℃ for a period of time, standing for layering, retaining an upper layer solution, adding the alkane solvent into a lower layer solution again for repeated extraction, and combining the obtained upper layer solution to obtain an extraction solution;
And S4, crystallizing and drying the extraction solution to obtain the triphenyl phosphate.
The invention firstly washes and extracts the 7-ACCA waste liquid to obtain an upper oil phase solution, and removes 2-picoline hydrochloride in the waste liquid; then adjusting the oil phase solution to be alkaline, and then carrying out distillation treatment to remove dichloromethane/isobutanol to obtain concentrated solution; and extracting the concentrated solution with an alkane solvent at a specific temperature to recover triphenyl phosphate, and crystallizing the extract to obtain triphenyl phosphate. The triphenyl phosphate obtained after the treatment can meet the requirements of electronic materials and medical intermediates, and the yield can reach more than 65%.
In the step S4, an adsorbent is added to the extraction solution to decolorize, and after filtering to obtain a filtrate, the filtrate is crystallized and dried to obtain triphenyl phosphate; or recrystallizing the extraction solution twice and drying to obtain the triphenyl phosphate. Wherein the decoloring agent is preferably activated carbon.
When the extraction solution is directly subjected to crystallization treatment without decolorization or is subjected to decolorization treatment by adopting silica gel and adsorption resin, the yield of the extraction solution can reach 89.9%, and when the extraction solution is decolorized by adopting silica gel, the yield can reach more than 89%, and when the extraction solution is decolorized by adopting adsorption resin, the yield can only reach 72.4%; however, the treatment can only obtain white-like products, and can only meet the use of flame retardant materials; when the activated carbon is adopted for decoloring treatment or the secondary recrystallization is adopted for decoloring treatment, white solid can be obtained, the white solid can not only meet the requirements of flame retardant materials, but also meet the requirements of electronic materials and pharmaceutical intermediates, and when the activated carbon is adopted for decoloring, the yield can reach 89.2%, and when the secondary recrystallization is adopted, the yield can only reach 82.9%.
In a preferred embodiment of the present invention, in the step S1, the volume ratio of the 7-ACCA waste liquid to the water is 3-5:1.
In a preferred embodiment of the present invention, in the step S2, the regulator may be one or a mixture of several bases selected from the group consisting of liquid base, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
In a preferred embodiment of the present invention, in the step S2, the parameters of the reduced pressure concentration of the washing solution are: concentrating under reduced pressure under vacuum degree of-0.09-0.1 Mpa until the washing solution is extracted at 140-160deg.C without fraction.
In a preferred embodiment of the present invention, in the step S3, the alkane solvent includes one of cyclohexane, n-heptane, n-hexane, isooctane, petroleum ether, and n-pentane.
The inventor adopts alkane solvent, ethyl acetate, toluene and the like to extract and recycle triphenyl phosphate, and discovers that white products which can meet the requirements of flame retardant materials and electronic materials and pharmaceutical intermediates can be obtained after alkane extraction, and the yield can reach more than 89 percent, and can not obtain qualified white or white-like products when other reagents are adopted for extraction.
In a preferred embodiment of the present invention, in the step S3, a volume ratio of the concentrated solution to the alkane solvent is 1:3-6.
In a preferred embodiment of the present invention, in the step S3, the alkane solvent is added to the concentrated solution and mixed uniformly, and then dissolved at 30 to 40 ℃ for 0.5 to 1.5 hours.
It should be noted that in this step, the extraction and dissolution temperature is strictly controlled, and only when the temperature is in the range of 30 to 75 ℃, a white or white-like acceptable product can be obtained, and when the temperature is too high, the quality of the obtained product is deteriorated.
In a preferred embodiment of the present invention, in the step S4, the volume/mass ratio of the extraction solution to the activated carbon is 1000:1-5, preferably 1000:2.5. wherein the unit of volume is L and the unit of mass is Kg.
In a preferred embodiment of the present invention, in the step S4, the activated carbon is decolorized under the following conditions: the decolorization temperature is 40-45 ℃, the filtrate is kept at 10-15 ℃ to separate out crystals, and the crystals are dried to obtain the product; or (b)
The conditions for decoloring the resin are as follows: the decoloring temperature is 65-75 ℃, the filtrate is kept at 10-15 ℃ to separate out crystals, and the crystals are dried to obtain the product.
As a preferred embodiment of the present invention, the method of two recrystallisation is: and (3) carrying out crystallization suction filtration on the extraction solution obtained in the step (S3), repeating the step (S3) and the crystallization suction filtration step again, and drying to obtain the product.
The method provided by the invention can obtain high-quality triphenyl phosphate without repeated refining, and has the advantages of high treatment efficiency, simplicity in operation, low treatment cost and suitability for recycling large-scale industrial waste liquid.
Detailed Description
7-ACCA is an important intermediate in the process of synthesizing cefaclor, waste liquid is generated in the process of synthesizing 7-ACCA, the main components in the waste liquid of 7-ACCA are methylene dichloride, chloroform, methanol, ethyl acetate, isobutanol, 2-methylpyridine and triphenyl phosphate, wherein the content of the triphenyl phosphate is generally about 10 percent, and if the triphenyl phosphate in the waste liquid of 7-ACCA cannot be recovered, a large amount of phosphorus-containing waste is generated, the treatment difficulty is high and the damage to the environment is easy to cause, and the resource waste is caused. Therefore, how to recover triphenyl phosphate from 7-ACCA becomes a problem to be solved urgently, but the recovery method in the prior art has low recovery efficiency and high recovery cost, and the recovered triphenyl phosphate has low purity and poor color and cannot be directly applied to electronic materials and medical intermediates.
The present invention will be described in further detail with reference to specific examples so as to more clearly understand the present invention by those skilled in the art.
Example 1
The embodiment provides a method for recycling triphenyl phosphate in 7-ACCA waste liquid, which comprises the following steps:
step S1, 5000mL of the triphenyl phosphate-containing mother liquor (the triphenyl phosphate content is about 10%) of the 7-ACCA product is added with 1000mL of tap water for washing for 3 times, layering is carried out, and the upper oil phase solution (namely a washing solution) is sampled and detected to have the 2-methyl pyridine content less than or equal to 0.1%.
And S2, regulating the pH value of the upper oil phase solution (washing solution) to be more than or equal to 7 by using a sodium hydroxide solution, concentrating under reduced pressure to be no fraction at 140-150 ℃ under the condition of 0.09-0.1 Mpa, keeping reduced pressure distillation for 30 minutes, and keeping 510mL of substrate (concentrated solution) as black oily liquid.
And S3, cooling the substrate (concentrated solution) to room temperature, adding 2000mL of cyclohexane, heating to 40 ℃ in a water bath, preserving heat, stirring for 30 minutes, standing for layering, retaining an upper layer solution, adding 1000mL of cyclohexane into a lower layer solution, continuously preserving heat and dissolving for 30 minutes at 40 ℃, standing for layering again, repeating for 2 times, treating the lower layer solution as waste liquid, combining and mixing the upper layer solution to obtain an extraction solution, and obtaining a light yellow color.
And S4, adding 8kg of active carbon into the extraction solution, preserving heat for 30 minutes at 40 ℃, carrying out hot filtration, cooling the filtrate to 10 ℃, preserving heat and growing crystals for 1 hour, carrying out suction filtration to obtain a white solid, and carrying out vacuum drying at 45 ℃ to obtain a finished product, wherein the purity is 99.66%, the dry loss is 0.06%, and the yield is 89.3% by taking the solid for detection.
Example 2
The embodiment provides a method for recycling triphenyl phosphate in 7-ACCA waste liquid, which comprises the following steps:
step S1, 5000mL of the triphenyl phosphate-containing mother liquor (the triphenyl phosphate content is about 10%) of the 7-ACCA product is added with 1000mL of tap water for washing for 3 times, layering is carried out, and the upper oil phase solution (namely a washing solution) is sampled and detected to have the 2-methyl pyridine content less than or equal to 0.1%.
And S2, regulating the pH value of the upper oil phase solution (washing solution) to be more than or equal to 7,0.09 to minus 0.1MPa by using a sodium hydroxide solution, concentrating under reduced pressure until no fraction is generated at 150-160 ℃, and keeping reduced pressure distillation for 30 minutes, wherein 510mL of substrate (concentrated solution) remains and is black oily liquid.
And S3, cooling the substrate (concentrated solution) to room temperature, adding 2000mL of cyclohexane, heating to 70 ℃ in a water bath, preserving heat, stirring for 30 minutes, standing for layering, retaining an upper layer solution, adding 1000mL of cyclohexane into a lower layer solution, continuously preserving heat and dissolving for 30 minutes at 70 ℃, standing for layering again, repeating for 2 times, treating the lower layer solution as waste liquid, combining and mixing the upper layer solution to obtain an extraction solution, and turning yellow.
And S4, adding 8kg of active carbon into the extraction solution, preserving heat for 30 minutes at 70 ℃, carrying out hot filtration, cooling the filtrate to 10 ℃, preserving heat and growing crystals for 1 hour, carrying out suction filtration to obtain an off-white solid, and carrying out vacuum drying at 45 ℃ to obtain a finished product, wherein the purity is 99.16%, the dry loss is 0.09%, and the yield is 91.2% by taking the solid for detection.
Example 3
The difference between this example and example 2 is that n-heptane is used as the extraction solvent in step S3, and finally a white needle-like solid is obtained, and the purity is 99.7% and the yield is 89.9% by solid detection.
Example 4
The difference between this example and example 2 is that petroleum ether is used as the extraction solvent in step S3, and finally white needle-like solid is obtained, and the purity is 99.3% and the yield is 90.6% by taking solid for detection.
Example 5
The difference between this example and example 3 is that the extraction temperature in step S3 is 30 ℃, and finally a white needle-like solid is obtained, and the purity is 99.6% and the yield is 65.2% by taking solid detection.
Example 6
The difference between this example and example 3 is that the extraction temperature in step S3 is 40 ℃, and finally a white needle-like solid is obtained, the purity is 99.6% and the yield is 89.9% as measured by taking the solid.
Example 7
The difference between this example and example 3 is that the extraction temperature in step S3 is 60 ℃, and finally a white needle-like solid is obtained, the purity is 99.1% and the yield is 92.6% by solid detection.
Example 8
The present embodiment differs from embodiment 3 in that the decoloring treatment is not performed in step S4.
The method comprises the following specific steps: directly performing hot filtration on the extraction solution, cooling the filtrate to 10 ℃, preserving heat and growing crystals for 1h, performing suction filtration, and then performing vacuum drying at 45 ℃ to obtain a finished product, and finally obtaining an off-white needle-like solid, wherein the purity is 99.4% and the yield is 89.9% by taking solid detection.
Example 9
The difference between this example and example 3 is that the decolorizing in step S4 is performed by silica gel, and the specific steps are as follows: adding 8kg of silica gel into the extraction solution, preserving heat for 30 minutes at 70 ℃, carrying out hot filtration, cooling the filtrate to 10 ℃, preserving heat and growing crystals for 1 hour, carrying out suction filtration, and then carrying out vacuum drying at 45 ℃ to obtain a finished product, and finally obtaining an off-white needle-like solid, wherein the purity is 99.4% and the yield is 89.6% by taking the solid for detection.
Example 10
The difference between this embodiment and embodiment 3 is that the secondary recrystallization is adopted in step S4, and the specific steps are as follows: cooling the extraction solution to 10 ℃, preserving heat, growing crystals for 1 hour, carrying out suction filtration to obtain wet product crystals, repeating the step S3 and the crystallization step, and carrying out vacuum drying at 45 ℃ to obtain a finished product, finally obtaining a white solid, taking the solid for detection, wherein the purity is 99.7%, and the yield is 82.9%.
Example 11
The difference between this example and example 3 is that the decolorizing is performed by using the adsorption resin in step S4, and the specific steps are as follows: 8kg of adsorption resin is added into the extraction solution, the temperature is kept for 30min at 70 ℃, hot filtration is carried out, the temperature of the filtrate is reduced to 10 ℃, the temperature is kept for crystal growth for 1h, after suction filtration, vacuum drying is carried out at 45 ℃ to obtain a finished product, finally, an off-white solid is obtained, the purity is 99.7% and the yield is 72.4% when the solid is detected.
Comparative example 1
The difference between this comparative example and example 1 is that in step S3 ethyl acetate was used as the extraction solvent, and the final brown viscous solid was obtained, which was measured as 78.3% pure.
Comparative example 2
The difference between this comparative example and example 1 is that toluene was used as the extraction solvent in step S3, and the final product was a brown solid powder, which was measured as a solid with a purity of 85.6%.
Comparative example 3
The difference between this comparative example and example 3 is that the extraction temperature in step S3 is 80 ℃, and finally a pale yellow solid is obtained, the purity is 99.13% and the yield is 92.9% as measured by taking the solid.
The results of the purities and yields of examples 1 to 11 and comparative examples 1 to 3 are summarized in Table 1 below:
TABLE 1
| Purity (%) | Yield (%) | Loss on dry | Appearance of | |
| Example 1 | 99.66％ | 89.3％ | 0.06％ | White solid |
| Example 2 | 99.16％ | 91.2％ | 0.09％ | Off-white solid |
| Example 3 | 99.7％ | 89.9％ | - | White needle-like solid |
| Example 4 | 99.3％ | 90.6％ | - | White needle-like solid |
| Example 5 | 99.6％ | 65.2％ | - | White needle-like solid |
| Example 6 | 99.6％ | 89.9％ | - | White needle-like solid |
| Example 7 | 99.1％ | 92.6％ | - | White needle-like solid |
| Example 8 | 99.4％ | 89.6％ | - | Quasi-white needle-like solid |
| Example 9 | 99.4％ | 89.9％ | - | Quasi-white needle-like solid |
| Example 10 | 99.7％ | 82.9％ | - | White solid |
| Example 11 | 99.7％ | 72.4％ | - | Off-white solid |
| Comparative example 1 | 78.3％ | - | - | Brown sticky solid |
| Comparative example 2 | 85.6％ | - | - | Brown solid powder |
| Comparative example 3 | 99.13％ | 92.9％ | - | Pale yellow solid |
From the above analysis, it can be seen that:
(1) The method of the invention is adopted for recovery treatment, thus obtaining white or white-like product triphenyl phosphate, the purity of which can reach more than 99%, the yield can reach more than 65%, and the dry loss is lower than 0.2%;
(2) When the extraction solution is directly subjected to crystallization treatment without decolorization or is subjected to decolorization treatment by adopting silica gel and adsorption resin, only white-like products can be obtained, the products can only meet the requirements of flame retardant materials, and when the extraction solution is directly subjected to crystallization treatment without decolorization, the yield can reach 89.9%, and when the extraction solution is subjected to decolorization by adopting silica gel, the yield can reach more than 89%, but when the extraction solution is subjected to decolorization by adopting adsorption resin, the yield can only reach 72.4%;
(3) When the method adopts activated carbon to carry out decolorization treatment or adopts a secondary recrystallization mode to carry out decolorization treatment, white solid can be obtained, the white solid can not only meet the requirements of flame retardant materials, but also meet the requirements of electronic materials and pharmaceutical intermediates, and when the method adopts activated carbon to carry out decolorization, the yield can reach 89.2 percent, and when the method adopts the secondary recrystallization mode, the yield can only reach 82.9 percent;
(4) The white product which can meet the requirements of flame-retardant materials and electronic materials and pharmaceutical intermediates can be obtained after alkane extraction, and the yield can reach more than 89 percent;
(5) When alkane is extracted, the extraction and dissolution temperature needs to be strictly controlled, white or white-like qualified products can be obtained only when the temperature is within the range of 30-75 ℃, and when the temperature is too high, such as 80 ℃, the quality of the obtained products is poor, the requirements of customers are difficult to meet, and when the temperature is too low, the yield is obviously reduced.
(6) The inventor finds that when the temperature of alkane extraction is 40-70 ℃, the yield is ensured to be more than 89%, and high-quality white products can be ensured to be obtained.
The foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recycling triphenyl phosphate in 7-ACCA waste liquid, which is characterized by comprising the following steps:
S1, adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing a lower water phase solution, and retaining an upper oil phase solution to obtain a washing solution;
S2, regulating the pH value of the washing solution by using a regulator to ensure that the pH value of the washing solution is more than or equal to 7, and concentrating under reduced pressure until no fraction is produced to obtain a concentrated solution;
S3, adding an alkane solvent into the concentrated solution, keeping the temperature at 30-75 ℃ for a period of time, standing for layering, reserving an upper layer solution, adding the alkane solvent into a lower layer solution again for repeated extraction, and combining the obtained upper layer solution to obtain an extraction solution, wherein the alkane solvent is one of cyclohexane, n-heptane, isooctane and petroleum ether;
And S4, crystallizing and drying the extraction solution to obtain the triphenyl phosphate.
2. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S4, an adsorbent is added to the extraction solution for decolorization, and after filtering to obtain a filtrate, the filtrate is crystallized and dried to obtain triphenyl phosphate.
3. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S4, the extraction solution is crystallized twice and dried to obtain triphenyl phosphate.
4. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S1, the volume ratio of the 7-ACCA waste liquid to water is 3-5:1.
5. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S2, the parameters of the reduced pressure concentration of the washing solution are: concentrating under reduced pressure under vacuum degree of-0.09 to-0.1 Mpa until the washing solution is extracted at 140-160deg.C without fraction.
6. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S3, the volume ratio of the concentrated solution to the alkane solvent is 1:3-6.
7. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 1, wherein in the step S3, the alkane solvent is added to the concentrated solution and mixed uniformly, and then the concentrated solution is dissolved at 40-50 ℃ while keeping the temperature and then is allowed to stand for delamination.
8. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 2, wherein in the step S4, the adsorbent is activated carbon, and the volume/mass ratio of the extraction solution to the activated carbon is 1000:1-5.
9. The method for recovering triphenyl phosphate from 7-ACCA waste liquid according to claim 2, wherein in the step S4, the adsorbent is activated carbon, and the condition for decolorizing the activated carbon is as follows: the decoloring temperature is 40-45 ℃, the filtrate is kept at 10-15 ℃ to separate out crystals, and the crystals are dried to obtain the product.
10. The method for recovering triphenyl phosphate from a 7-ACCA waste liquid according to claim 2, wherein in the step S4, the adsorbent is a resin, and the conditions for decolorizing the resin are as follows: and (3) keeping the decoloring temperature at 65-75 ℃, keeping the filtrate at 10-15 ℃ to separate out crystals, and drying the crystals to obtain the product.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1994591A (en) * | 1932-05-21 | 1935-03-19 | Eastman Kodak Co | Recovery of plasticizers from film scrap and like materials |
| US2059912A (en) * | 1936-04-08 | 1936-11-03 | Eastman Kodak Co | Refining of crude triphenylphosphate |
| CN101289464A (en) * | 2008-05-22 | 2008-10-22 | 浙江工业大学 | Process for recovering triphenyl phosphine oxide and 2-mercaptobenzothiazole from production waste liquid of cephalothin active ester |
| CN107236000A (en) * | 2017-06-06 | 2017-10-10 | 池正伟 | The recovery method of triphenyl phosphate |
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2021
- 2021-12-06 CN CN202111478261.0A patent/CN114195822B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1994591A (en) * | 1932-05-21 | 1935-03-19 | Eastman Kodak Co | Recovery of plasticizers from film scrap and like materials |
| US2059912A (en) * | 1936-04-08 | 1936-11-03 | Eastman Kodak Co | Refining of crude triphenylphosphate |
| CN101289464A (en) * | 2008-05-22 | 2008-10-22 | 浙江工业大学 | Process for recovering triphenyl phosphine oxide and 2-mercaptobenzothiazole from production waste liquid of cephalothin active ester |
| CN107236000A (en) * | 2017-06-06 | 2017-10-10 | 池正伟 | The recovery method of triphenyl phosphate |
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| Title |
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| 磷酸三苯酯残渣的回收工艺;张艳妙;《河北化工》;第30卷(第5期);69 * |
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