CN114195822A - Method for recycling triphenyl phosphate in 7-ACCA waste liquid - Google Patents
Method for recycling triphenyl phosphate in 7-ACCA waste liquid Download PDFInfo
- Publication number
- CN114195822A CN114195822A CN202111478261.0A CN202111478261A CN114195822A CN 114195822 A CN114195822 A CN 114195822A CN 202111478261 A CN202111478261 A CN 202111478261A CN 114195822 A CN114195822 A CN 114195822A
- Authority
- CN
- China
- Prior art keywords
- solution
- triphenyl phosphate
- acca
- waste liquid
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 41
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title description 3
- 238000000605 extraction Methods 0.000 claims abstract description 44
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003463 adsorbent Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 238000004042 decolorization Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 3
- 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
- 239000003054 catalyst Substances 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 12
- 238000007670 refining Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 38
- 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
- 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
- 238000001816 cooling Methods 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 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
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 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
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012452 mother liquor Substances 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
- 238000005070 sampling Methods 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
- OQSAFIZCBAZPMY-UHFFFAOYSA-N 7-azaniumyl-3-chloro-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylate Chemical group S1CC(Cl)=C(C(O)=O)N2C(=O)C(N)C21 OQSAFIZCBAZPMY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 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
- 239000002440 industrial waste Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 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
- 230000002194 synthesizing effect Effects 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 recovering triphenyl phosphate from 7-ACCA waste liquid, which comprises the following steps: adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing the lower-layer aqueous phase solution, and retaining the upper-layer 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 extracted; adding an alkane solvent into the concentrated solution, uniformly mixing, standing for layering, retaining an upper layer solution, adding the alkane solvent into a lower layer solution again for repeated extraction, and combining and mixing the obtained upper layer solution; and crystallizing and drying the extraction solution to obtain triphenyl phosphate. The method for recovering triphenyl phosphate from 7-ACCA waste liquid provided by the invention has the advantages of simple process, high recovery rate and low recovery cost, and can obtain high-quality triphenyl phosphate without repeated refining.
Description
Technical Field
The invention belongs to the technical field of byproduct recovery, and particularly relates to a method for recovering triphenyl phosphate from 7-ACCA waste liquid.
Background
7-ACCA, chemical name is 7-amino-3-chloro-3-cephem-4-carboxylic acid, and is an important intermediate in the synthesis process of cefaclor. In the process of synthesizing 7-ACCA, waste liquid is generated, and the waste liquid contains a large amount of triphenyl phosphate byproducts, and if the byproducts cannot be recycled, the byproducts can cause a large amount of phosphorus-containing solid wastes, so that the harmless treatment difficulty is high, and the resource waste is caused.
Triphenyl phosphate is an important chemical intermediate and is widely applied in the fields of flame retardant materials, electronic materials, pharmaceutical intermediates, plasticized materials and the like. At present, triphenyl phosphate recovery often has the problems of low purity and color difference, is difficult to meet the requirements of electronic materials and medical intermediates, and can meet the requirements only by repeatedly refining for many times, so that the recovery rate of triphenyl phosphate is lower, and the recovery cost is higher.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an efficient and low-cost recovery method, high-quality triphenyl phosphate can be recovered from 7-ACCA waste liquid, the purity of the recovered triphenyl phosphate is high, the color is good, and the requirements of flame retardant materials and/or electronic materials and pharmaceutical intermediates can be met.
The invention provides a method for recovering triphenyl phosphate from 7-ACCA waste liquid, which comprises the following steps:
step S1, adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing the lower-layer aqueous phase solution, and reserving the upper-layer oil phase solution to obtain a washing solution;
step S2, adjusting 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 extracted to obtain a concentrated solution;
step S3, adding an alkane solvent into the concentrated solution, keeping the temperature for a period of time at 30-75 ℃, standing for layering, retaining the upper layer solution, adding the alkane solvent into the lower layer solution again for repeated extraction, and combining the obtained upper layer solutions to obtain an extraction solution;
and step S4, crystallizing and drying the extraction solution to obtain triphenyl phosphate.
The method comprises the steps of firstly, washing and extracting 7-ACCA waste liquid to obtain an upper oil phase solution, and removing 2-methylpyridine 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 a concentrated solution; and (3) extracting the concentrated solution by adopting an alkane solvent at a specific temperature to recover triphenyl phosphate, and finally 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%.
As a preferred embodiment of the present invention, in step S4, an adsorbent is added to the extraction solution for decolorization, after filtration 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 decolorizing agent is preferably activated carbon.
Wherein, when the extraction solution is directly crystallized without decolorization or is decolorized by silica gel and adsorbent resin, the yield can reach 89.9%, when the extraction solution is decolorized by silica gel, the yield can also reach more than 89%, and when the extraction solution is decolorized by adsorbent resin, the yield can only reach 72.4%; however, the treatment can only obtain a white-like product, and can only meet the use of flame-retardant materials; when the activated carbon is adopted for decoloring or the secondary recrystallization mode is adopted for decoloring, white solid can be obtained, the white solid can meet the requirements of flame-retardant materials and electronic materials and pharmaceutical intermediates, the yield can reach 89.2% when the activated carbon is adopted for decoloring, and the yield can only reach 82.9% when the secondary recrystallization mode is adopted.
In a preferred embodiment of the present invention, in step S1, the volume ratio of the 7-ACCA waste liquid to water is 3-5: 1.
In a preferred embodiment of the present invention, in step S2, the modifier may be one or more of liquid alkali, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
In a preferred embodiment of the present invention, in step S2, the parameters of the washing solution concentration under reduced pressure are: concentrating under reduced pressure under the vacuum degree of-0.09 to-0.1 Mpa until the washing solution is extracted without fraction under the conditions of 140 ℃ and 160 ℃.
In a preferred embodiment of the present invention, in step S3, the alkane solvent includes one of cyclohexane, n-heptane, n-hexane, isooctane, petroleum ether, and n-pentane.
The inventor simultaneously adopts alkane solvents, ethyl acetate, toluene and the like to extract and recover triphenyl phosphate, and finds that white products which can meet the requirements of flame-retardant materials and electronic materials and pharmaceutical intermediates can be obtained after the alkane is extracted, the yield can reach more than 89%, and qualified white or off-white products can not be obtained when other reagents are used for extraction.
In a preferred embodiment of the present invention, in step S3, the volume ratio of the concentrated solution to the alkane solvent is 1: 3-6.
In a preferred embodiment of the present invention, in 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 30-75 ℃, white or off-white qualified products can be obtained, and when the temperature is too high, the quality of the obtained products is deteriorated.
In a preferred embodiment of the present invention, in step S4, the volume-to-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 step S4, the activated carbon decoloring conditions are as follows: decolorizing at 40-45 deg.C, maintaining the filtrate at 10-15 deg.C to separate out crystal, and drying the crystal; or
The resin decoloring conditions are as follows: and (3) decoloring at 65-75 ℃, keeping the filtrate at 10-15 ℃ to separate out crystals, and drying the crystals to obtain the catalyst.
In a preferred embodiment of the present invention, the method of twice recrystallization comprises: and (5) after the extraction solution obtained in the step S3 is crystallized and filtered, repeating the step S3 and the step of crystallization and filtering 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, simple operation, low treatment cost and suitability for large-scale industrial waste liquid recovery treatment.
Detailed Description
7-ACCA is an important intermediate in the synthesis process of cefaclor, waste liquor can be generated in the synthesis process of 7-ACCA, the main components in the 7-ACCA waste liquor are dichloromethane, chloroform, methanol, ethyl acetate, isobutanol, 2-methylpyridine and triphenyl phosphate, wherein the content of the triphenyl phosphate is about 10%, if triphenyl phosphate in the 7-ACCA waste liquor cannot be recovered, on one hand, a large amount of phosphorus-containing waste can be generated, the treatment difficulty is high, the environment is easily damaged, and on the other hand, the resource waste is caused. Therefore, how to recover triphenyl phosphate from 7-ACCA becomes a problem to be solved urgently, and the recovery method in the prior art has low recovery efficiency and high recovery cost, and the triphenyl phosphate obtained by recovery has low purity and poor color, and cannot be directly applied to electronic materials and medical intermediates.
The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.
Example 1
The embodiment provides a method for recovering triphenyl phosphate from 7-ACCA waste liquid, which comprises the following steps:
step S1, 5000mL of a 7-ACCA product triphenyl phosphate mother liquor (triphenyl phosphate content is about 10%) is added with 1000mL of tap water to be washed for 3 times, layering is carried out, and the content of 2-methylpyridine is less than or equal to 0.1% through sampling and detecting an upper oil phase solution (namely a washing solution).
And step S2, adjusting 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 at-0.09 to-0.1 Mpa until no fraction is obtained at 140-150 ℃, keeping reduced pressure distillation for 30 minutes, and leaving 510mL of substrate (concentrated solution) as black oil liquid.
And step S3, cooling the substrate (concentrated solution) to room temperature, adding 2000mL of cyclohexane, heating in a water bath to 40 ℃, keeping the temperature and stirring for 30 minutes, standing for layering, keeping the upper layer solution, adding 1000mL of cyclohexane into the lower layer solution, keeping the temperature and dissolving for 30 minutes at 40 ℃, standing for layering again, treating the lower layer solution as waste liquid after repeating for 2 times, combining and mixing the upper layer solution to obtain an extraction solution which is light yellow.
Step S4, adding 8kg of activated carbon into the extraction solution, preserving heat for 30 minutes at 40 ℃, carrying out heat filtration, cooling the filtrate to 10 ℃, preserving heat for growing crystals for 1 hour, carrying out suction filtration to obtain a white solid, carrying out vacuum drying at 45 ℃ to obtain a finished product, and detecting the solid to obtain a product with the purity of 99.66%, the dry loss of 0.06% and the yield of 89.3%.
Example 2
The embodiment provides a method for recovering triphenyl phosphate from 7-ACCA waste liquid, which comprises the following steps:
step S1, 5000mL of a 7-ACCA product triphenyl phosphate mother liquor (triphenyl phosphate content is about 10%) is added with 1000mL of tap water to be washed for 3 times, layering is carried out, and the content of 2-methylpyridine is less than or equal to 0.1% through sampling and detecting an upper oil phase solution (namely a washing solution).
And step S2, adjusting 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 under the condition of 0.09-minus 0.1MPa to obtain no fraction at 150-160 ℃, keeping reduced pressure distillation for 30 minutes, and leaving 510mL of substrate (concentrated solution) as black oil liquid.
And step S3, cooling the substrate (concentrated solution) to room temperature, adding 2000mL of cyclohexane, heating in a water bath to 70 ℃, keeping the temperature and stirring for 30 minutes, standing for layering, keeping the upper layer solution, adding 1000mL of cyclohexane to the lower layer solution, keeping the temperature and dissolving for 30 minutes at 70 ℃, standing for layering again, treating the lower layer solution as waste liquid after repeating for 2 times, combining and mixing the upper layer solution to obtain an extraction solution which is yellow.
Step S4, adding 8kg of activated carbon into the extraction solution, preserving heat at 70 ℃ for 30 minutes, carrying out heat filtration, cooling the filtrate to 10 ℃, preserving heat for growing crystals for 1 hour, carrying out suction filtration to obtain a white-like solid, carrying out vacuum drying at 45 ℃ to obtain a finished product, and detecting the solid to obtain a product with the purity of 99.16%, the dry loss of 0.09% and the yield of 91.2%.
Example 3
This example differs from example 2 in that in step S3, n-heptane was used as the extraction solvent, and a white needle-like solid was obtained, which was checked for purity of 99.7% and yield of 89.9%.
Example 4
The difference between this example and example 2 is that in step S3, petroleum ether was used as the extraction solvent, and a white needle-like solid was obtained, which was tested to have a purity of 99.3% and a yield of 90.6%.
Example 5
This example differs from example 3 in that the extraction temperature in step S3 was 30 ℃, and a white needle-like solid was obtained, which was checked for purity of 99.6% and yield of 65.2%.
Example 6
This example differs from example 3 in that the extraction temperature in step S3 was 40 ℃, and a white needle-like solid was finally obtained, which was checked for purity of 99.6% and yield of 89.9%.
Example 7
This example differs from example 3 in that the extraction temperature in step S3 was 60 ℃, and a white needle-like solid was finally obtained, which was checked for purity of 99.1% and yield of 92.6%.
Example 8
This example is different from example 3 in that the decoloring treatment is not performed in step S4.
The method comprises the following specific steps: directly performing heat filtration on the extraction solution, cooling the filtrate to 10 ℃, maintaining the temperature and growing the crystals for 1h, performing suction filtration, and performing vacuum drying at 45 ℃ to obtain a finished product, and finally obtaining a white needle-like solid, wherein the purity is 99.4% and the yield is 89.9% by taking solid for detection.
Example 9
The difference between this embodiment and embodiment 3 is that silica gel is used for decoloring in step S4, and the specific steps are as follows: adding 8kg of silica gel into the extraction solution, keeping the temperature at 70 ℃ for 30 minutes, carrying out heat filtration, cooling the filtrate to 10 ℃, keeping the temperature and growing crystals for 1 hour, carrying out suction filtration, and carrying out vacuum drying at 45 ℃ to obtain a finished product, finally obtaining a white needle-like solid, wherein the purity is 99.4% and the yield is 89.6% by taking solid for detection.
Example 10
The present embodiment is different from embodiment 3 in that a secondary recrystallization manner is adopted in step S4, and the specific steps are as follows: cooling the extraction solution to 10 ℃, keeping the temperature for growing the crystals for 1 hour, filtering to obtain wet product crystals, repeating the step S3 and the crystallization step, and performing vacuum drying at 45 ℃ to obtain a finished product, wherein the finished product is finally obtained, and the solid is detected to have the purity of 99.7% and the yield of 82.9%.
Example 11
The difference between this example and example 3 is that in step S4, the adsorbent resin is used for decolorization, and the specific steps are as follows: adding 8kg of adsorbent resin into the extraction solution, keeping the temperature at 70 ℃ for 30min, carrying out heat filtration, cooling the filtrate to 10 ℃, keeping the temperature and growing the crystals for 1h, carrying out suction filtration, and carrying out vacuum drying at 45 ℃ to obtain a finished product, finally obtaining a white-like solid, wherein the purity is 99.7% and the yield is 72.4% by taking solid for detection.
Comparative example 1
This comparative example differs from example 1 in that ethyl acetate was used as the extraction solvent in step S3, and a brown viscous solid was finally obtained, which was checked for 78.3% purity.
Comparative example 2
This comparative example differs from example 1 in that toluene was used as the extraction solvent in step S3, and a brown solid powder was finally obtained, which was checked for solids and had a purity of 85.6%.
Comparative example 3
This comparative example differs from example 3 in that the extraction temperature in step S3 was 80 ℃, and a pale yellow solid was finally obtained, which was checked to have a purity of 99.13% and a yield of 92.9%.
The results of examples 1 to 11 and comparative examples 1 to 3, such as purity and yield, are summarized in Table 1 below:
TABLE 1
| Purity (%) | Yield (%) | Loss due to dryness | Appearance of the product | |
| 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 acicular solid |
| Example 4 | 99.3％ | 90.6％ | - | White acicular solid |
| Example 5 | 99.6％ | 65.2％ | - | White acicular solid |
| Example 6 | 99.6％ | 89.9％ | - | White acicular solid |
| Example 7 | 99.1％ | 92.6％ | - | White acicular solid |
| Example 8 | 99.4％ | 89.6％ | - | Off-white acicular solid |
| Example 9 | 99.4％ | 89.9％ | - | Off-white acicular 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 provided by the invention is adopted for recycling treatment, so that white or off-white triphenyl phosphate can be obtained, the purity of the triphenyl phosphate 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 crystallized without decoloring or is decolored by adopting silica gel and adsorbent resin, only a white-like product can be obtained, the product can only meet the use requirement of a flame-retardant material, and the yield can reach 89.9 percent when the extraction solution is directly crystallized without decoloring, while the yield can also reach more than 89 percent when the extraction solution is decolored by adopting silica gel, but the yield can only reach 72.4 percent when the extraction solution is decolored by adopting the adsorbent resin;
(3) when the activated carbon is adopted for decoloring or the secondary recrystallization mode is adopted for decoloring, white solid can be obtained, the white solid can meet the requirements of flame-retardant materials and electronic materials and pharmaceutical intermediates, the yield can reach 89.2% when the activated carbon is adopted for decoloring, and the yield can only reach 82.9% when the secondary recrystallization mode is adopted;
(4) white products which can meet the requirements of flame-retardant materials and electronic materials and pharmaceutical intermediates can be obtained after the extraction of the alkanes, and the yield can reach more than 89%;
(5) when the alkane is extracted, the extraction and dissolution temperature needs to be strictly controlled, white or off-white qualified products can be obtained only when the temperature is within the range of 30-75 ℃, when the temperature is too high, such as 80 ℃, the quality of the obtained products is deteriorated, the customer requirements are difficult to meet, and when the temperature is too low, the yield is obviously reduced.
(6) The inventor finds out through a large amount of experimental research that when the extraction temperature of the alkane is 40-70 ℃, the yield can be ensured to be more than 89%, and a high-quality white product can be ensured to be obtained.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement 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 recovering triphenyl phosphate from 7-ACCA waste liquid is characterized by comprising the following steps:
step S1, adding water into the 7-ACCA waste liquid, fully mixing, standing for layering, removing the lower-layer aqueous phase solution, and reserving the upper-layer oil phase solution to obtain a washing solution;
step S2, adjusting 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 extracted to obtain a concentrated solution;
step S3, adding an alkane solvent into the concentrated solution, keeping the temperature for a period of time at 30-75 ℃, standing for layering, retaining the upper layer solution, adding the alkane solvent into the lower layer solution again for repeated extraction, and combining the obtained upper layer solutions to obtain an extraction solution;
and step S4, crystallizing and drying the extraction solution to obtain triphenyl phosphate.
2. The method of claim 1, wherein in 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; or
And crystallizing the extraction solution twice and drying to obtain triphenyl phosphate.
3. The method of claim 1, wherein in step S1, the volume ratio of 7-ACCA waste liquid to water is 3-5: 1.
4. The method of claim 1, wherein in step S2, the parameters of the washing solution concentration under reduced pressure are: concentrating under reduced pressure under the vacuum degree of-0.09 to-0.1 Mpa until the washing solution is extracted without fraction under the conditions of 140 ℃ and 160 ℃.
5. The method of claim 1, wherein in step S3, the alkane solvent comprises one of cyclohexane, n-heptane, n-hexane, isooctane, petroleum ether, and n-pentane.
6. The method of claim 1, wherein in step S3, the volume ratio of the concentrated solution to the alkane solvent is 1: 3-6.
7. The method of claim 1, wherein in step S3, the alkane solvent is added to the concentrated solution and mixed uniformly, and the mixture is dissolved by holding at 40-50 ℃ and then allowed to stand for demixing.
8. The method of claim 1, wherein in the step S4, the volume-to-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 decolorizing condition of activated carbon is: decolorizing at 40-45 deg.C, maintaining the filtrate at 10-15 deg.C to separate out crystal, and drying the crystal; or
The resin decoloring conditions are as follows: and (3) decoloring at 65-75 ℃, keeping the filtrate at 10-15 ℃ to separate out crystals, and drying the crystals to obtain the catalyst.
10. The method for recovering triphenyl phosphate from 7-ACCA waste liquid according to claim 2, wherein the two-time crystallization method comprises: and (5) after the extraction solution obtained in the step S3 is crystallized and filtered, repeating the step S3 and the step of crystallization and filtering again, and drying to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111478261.0A CN114195822B (en) | 2021-12-06 | 2021-12-06 | Method for recycling triphenyl phosphate in 7-ACCA waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111478261.0A CN114195822B (en) | 2021-12-06 | 2021-12-06 | Method for recycling triphenyl phosphate in 7-ACCA waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114195822A true CN114195822A (en) | 2022-03-18 |
| CN114195822B CN114195822B (en) | 2024-04-26 |
Family
ID=80650720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111478261.0A Active CN114195822B (en) | 2021-12-06 | 2021-12-06 | Method for recycling triphenyl phosphate in 7-ACCA waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114195822B (en) |
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 |
-
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 |
Non-Patent Citations (1)
| Title |
|---|
| 张艳妙: "磷酸三苯酯残渣的回收工艺", 《河北化工》, vol. 30, no. 5, pages 69 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114195822B (en) | 2024-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110862362B (en) | Refining method of D-pantoic acid lactone | |
| CN108017535B (en) | Method for extracting long-chain dicarboxylic acid from fermentation liquor | |
| CN107522631A (en) | A kind of preparation method of occrycetin | |
| CN104140420A (en) | Synthesis process of thiothiamine | |
| CN114933288A (en) | High-purity monopotassium phosphate and preparation method thereof | |
| CN108997211A (en) | A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine | |
| CN108997424B (en) | Simple method for preparing fosfomycin trometamol | |
| CN114195822A (en) | Method for recycling triphenyl phosphate in 7-ACCA waste liquid | |
| US2178210A (en) | Isolation of leucine and tyrosine from corn gluten | |
| CN114957007B (en) | Method for recycling 3,5 methyl ester through alcoholysis of antioxidant 1010 | |
| CN111004131A (en) | Method for recovering sucralose by-product salt | |
| CN104355990A (en) | Method for recycling and mechanically using L- (+) -tartaric acid in D-ethyl ester production | |
| CN114014835A (en) | Glycolide purification process | |
| CN114933588A (en) | Refining method of rabeprazole sodium crude product | |
| CN110615749B (en) | Method for treating waste liquid from production of N-acetylcysteine | |
| CN1315777C (en) | Processes for the recovery of optically active diacyltartatic acids | |
| CN112159356A (en) | Racemization recovery method of dextromethorphan hydrobromide intermediate byproduct | |
| CN101643420A (en) | Method for reclaiming halogen acid salt of triethylamine in residue of synthesized vinylene carbonate | |
| CN114907348B (en) | Preparation method of 4-chloro-5-iodo-7H-pyrrolo [2,3-d ] pyrimidine | |
| CN111635419B (en) | Method for treating cefdinir refined mother liquor | |
| US5304677A (en) | Method for producing 2,6-dihydroxybenzoic acid | |
| US2380890A (en) | Preparation of glutamic acid hydrochloride | |
| CN109836398B (en) | Preparation method of special biological buffer-piperazine-diethylsulfonic acid 1.5Na salt | |
| EP0035759B1 (en) | Process for producing dithionites | |
| TWI851923B (en) | Method for producing recycled polyester chips from recycled polyester fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 441000 Xiangcheng Economic Development Zone, Xiangcheng District, Xiangyang City, Hubei Province Patentee after: Hubei Lingsheng Pharmaceutical Co.,Ltd. Country or region after: China Address before: 441000 Xiangcheng Economic Development Zone, Xiangcheng District, Xiangyang City, Hubei Province Patentee before: HUBEI LINGSHENG PHARMACEUTICAL CO.,LTD. Country or region before: China |
|
| CP03 | Change of name, title or address |