CN118063508A - Method for recovering triphenylphosphine oxide - Google Patents
Method for recovering triphenylphosphine oxide Download PDFInfo
- Publication number
- CN118063508A CN118063508A CN202311422564.XA CN202311422564A CN118063508A CN 118063508 A CN118063508 A CN 118063508A CN 202311422564 A CN202311422564 A CN 202311422564A CN 118063508 A CN118063508 A CN 118063508A
- Authority
- CN
- China
- Prior art keywords
- triphenylphosphine oxide
- solid
- liquid mixture
- mixing
- waste residue
- 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.)
- Pending
Links
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 68
- 239000000203 mixture Substances 0.000 claims description 59
- 239000002699 waste material Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- -1 triphenylphosphine oxide acetic acid Chemical compound 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 238000007239 Wittig reaction Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000004537 pulping Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000006751 Mitsunobu reaction Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of material recovery, and particularly relates to a separation and purification technology of triphenylphosphine oxide as a byproduct of a wittig reaction. The method for recycling triphenylphosphine oxide has the advantages of simple process steps, short production period, high raw material conversion rate and low cost, and greatly reduces labor operation and energy consumption; the invention has high conversion rate of raw materials, good quality of recovered products, high yield and convenient post-treatment, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of material recovery, and particularly relates to a separation and purification technology of triphenylphosphine oxide as a byproduct of a wittig reaction.
Background
In chemical synthesis, the Wittig reaction and the mitsunobu reaction tend to produce a large amount of by-product triphenylphosphine oxide. The triphenylphosphine oxide skeleton has rigidity, oxygen atoms have alkalinity, and are easy to induce crystallization and oxidation-reduction reaction with other substances, or are combined with metal atoms to form a complex. Because of the special physical and chemical properties of triphenylphosphine oxide, the separation and purification difficulty of by-products containing triphenylphosphine oxide is high in industrial production, especially the cephalosporin waste residue contains triphenylphosphine oxide, and simultaneously contains a large amount of complex organic impurity components, so that high-quality triphenylphosphine oxide is difficult to separate and purify.
At present, most of the separation and purification methods of the triphenylphosphine oxide are concentration and crystallization combination or extraction-concentration and crystallization combination, or complex is formed by combining the triphenylphosphine oxide with metal atoms, and then extraction-concentration and crystallization are carried out. Chinese patent No. CN109232581a discloses that by-product triphenylphosphine oxide from the reaction of zinc chloride and Mitsunobu forms a strong complex, which is filtered to remove the complex of triphenylphosphine oxide and zinc chloride; CN106967071a discloses that triphenylphosphine oxide, a byproduct of Mitsunobu reaction, is utilized to form a complex precipitate, and triphenylphosphine oxide can be removed by filtration; CN101481389a discloses that precipitation is formed by the addition reaction of concentrated sulfuric acid and triphenylphosphine oxide, and is separated from the organic solvent. By further processing the filter residue and the filtrate, triphenylphosphine oxide and triphenylphosphine with higher purity can be separated; CN109354595A discloses a method for recovering triphenylphosphine oxide from Wittig reaction rectification residual liquid, which uses Wittig reaction rectification residual liquid as raw material, firstly obtaining crude product by water separation crystallization and crystal growth, and then obtaining triphenylphosphine oxide by purification; CN112409409A utilizes triphenylphosphine oxide and complexing agent to perform eutectic precipitation reaction, and the generated eutectic substance has very small solubility in a second solvent so as to realize separation and purification of triphenylphosphine oxide and impurities; dissolving triphenylphosphine oxide in a second solvent, regulating the pH value to 8-9, separating the triphenylphosphine oxide from a salt containing complex ions (complex salt) after solid-liquid separation, concentrating the filtrate, pulping to purify, and obtaining the triphenylphosphine oxide with higher purity; US6011181a provides a process for reducing the level of trisubstituted phosphine, arsenic and/or oxidized hydrogen sulfide from a mixture comprising the desired product and at least one such oxide, comprising adding a metal salt to the mixture to form a complex with the oxide, and removing the complex from the mixture. This method has particular utility for removing triphenylphosphine oxide from a mixture. Triphenylphosphine oxide was conveniently removed by precipitation with ZnCl 2 in ethanol, volume 82 of literature Donald C.Batesky et al..Removal of Triphenylphosphine Oxide by Precipitation with Zinc Chloride in Polar Solvents."J.Org.Chem.".2017,. This precipitation works in polar organic solvents such as EtOAc, praac and' praoh and is tolerant of many common functionalities including alcohols, aldehydes, amides and some nitrogen heterocycles. It is expected that this process will provide an additional purification tool for many reactions that use triphenylphosphine as a reducing agent.
However, the triphenylphosphine oxide obtained by the method has low recovery rate and poor quality, and a large amount of organic solvents and metal complexing agents are used, so that the process steps are complex and the recovery cost is high. Therefore, the invention provides a separation and purification technology of triphenylphosphine oxide as a byproduct of wittig and other reactions, and the method is used for recovering triphenylphosphine oxide, and has the advantages of simple process steps, short production period, high raw material conversion rate, low cost and greatly reduced labor operation and energy consumption; the invention has high conversion rate of raw materials, good quality of recovered products, high yield and convenient post-treatment, and is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a separation and purification technology of triphenylphosphine oxide as a byproduct of a wittig reaction, and the separation and purification technology provided by the invention is adopted: high efficiency, green, low cost, and high recovery rate and good quality of the obtained triphenylphosphine oxide.
Specifically, in order to achieve the above object, the present invention provides the following technical solutions:
Mixing the reaction byproduct triphenylphosphine oxide waste residue with water, and mixing the obtained waste residue liquid with acid for reaction to obtain a primary solid-liquid mixture;
mixing solid matters obtained by solid-liquid separation of the primary solid-liquid mixture with water, regulating the pH value of a mixed system to 9-11 by alkali, and reacting to obtain a secondary solid-liquid mixture;
And (3) carrying out solid-liquid separation on the secondary solid-liquid mixture to obtain a solid phase, namely the triphenylphosphine oxide.
One embodiment of the recovery method is as follows:
Mixing triphenylphosphine oxide waste residue with water, mixing the obtained waste residue liquid with acetic acid, adjusting the pH value to 2-5.5, and reacting to obtain a primary solid-liquid mixture; mixing the solid substance obtained by solid-liquid separation of the primary solid-liquid mixture with water, and regulating the pH value of the mixed system to 9-11 by alkali for reaction to obtain a secondary solid-liquid mixture; and carrying out solid-liquid separation on the secondary solid-liquid mixture to obtain a solid phase, namely the triphenylphosphine oxide.
In the recovery method, the acid is acetic acid, hydrochloric acid, acetic acid, sulfuric acid and formic acid, and the alkali is sodium hydroxide and sodium bicarbonate.
Preferably, the molar ratio of triphenylphosphine oxide to acid in the waste residue solution is 1: (0.5-3).
Preferably, the acidification reaction temperature is 70-80 ℃ and the time is 4-8 h.
The acidification reaction is followed by a cooling process, wherein the cooling temperature is 25-40 ℃.
Preferably, the beating speed is 80-150 rpm, and the beating time is 30-60 min.
The invention provides a triphenylphosphine oxide separation and purification technology, which comprises the following steps: mixing triphenylphosphine oxide waste residue with water, mixing the obtained waste residue liquid with acid, adjusting the pH value to 2-5.5, and reacting to obtain a primary solid-liquid mixture; mixing the solid substance obtained by solid-liquid separation of the primary solid-liquid mixture with water, and regulating the pH value of the mixed system to 9-11 by alkali for reaction to obtain a secondary solid-liquid mixture; and carrying out solid-liquid separation on the secondary solid-liquid mixture to obtain a solid phase, namely the triphenylphosphine oxide.
The invention utilizes triphenylphosphine oxide to react with acid, and the generated complex has small solubility in water so as to realize separation and purification of triphenylphosphine oxide and impurities; and mixing the purified triphenylphosphine oxide with water, adjusting the pH value to 9-11, and carrying out solid-liquid separation to obtain the triphenylphosphine oxide with higher purity.
Specifically, the separation and purification technology of the present invention has the following advantages:
1) The method provided by the invention is used for recycling triphenylphosphine oxide, and the primary recycling rate is more than or equal to 85.5%;
2) The purity of the obtained triphenylphosphine oxide is more than or equal to 98.5%.
3) The solvent only uses water by adopting the method provided by the invention, the process is environment-friendly, and the recovery cost is low.
Therefore, the method provided by the invention is used for recycling the triphenylphosphine oxide, has high primary recycling rate, high purity of the triphenylphosphine oxide, low recycling cost, environment-friendly process and important industrialized application value.
The researchers of the present invention unexpectedly found that acetic acid could be used to separate and purify triphenylphosphine oxide with best effect, compared with other concentrated crystallization combinations or extraction-concentration, crystallization combinations, or combination with metal atoms to form complexes, re-extraction-concentration, crystallization. Unexpected technical effects are achieved, and the method is creative. And other types of acid are tried to obtain better separation and purification technical effects.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
The invention takes triphenylphosphine oxide waste residue as raw material, only water is used as solvent, the triphenylphosphine oxide waste residue can be converted into triphenylphosphine oxide with purity of more than 99% by two steps of reaction, and the yield is more than 85%, compared with the existing method for recovering triphenylphosphine oxide, the method has the advantages of simple process steps, mild reaction conditions, short production period, high raw material conversion rate and low cost, and greatly reduces labor operation and energy consumption; the invention has high conversion rate of raw materials, good quality of recovered products, high yield and convenient post-treatment, and is suitable for industrial production.
Drawings
FIG. 1 triphenylphosphine oxide HPLC profile
FIG. 2 is a magnetic spectrum of the triphenylphosphine oxide core
FIG. 3 LCMS spectrum of triphenylphosphine oxide
FIG. 4 nuclear magnetic spectrum of triphenylphosphine oxide and acetic acid complex
Detailed Description
In order to further illustrate the present invention, the method for recovering triphenylphosphine oxide provided by the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The reagents used in the examples are all commercially available; the triphenylphosphine oxide waste residue is a Wittig reaction mother liquor waste residue, and the main components of the triphenylphosphine oxide waste residue are triphenylphosphine oxide, wittig reaction intermediates, impurities, ethanol, water, isopropanol, isopropyl acetate and toluene; the impurities are not particularly limited and are well known in the art.
Example 1:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 53.32% (namely, 100g triphenylphosphine oxide waste residue contains 53.32g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding hydrochloric acid solution until the pH value is 2-5, reacting at 65-80 ℃ for 4 hours under heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing 96.3g of obtained filter cake with 200mL of water, stirring uniformly, then dropwise adding sodium carbonate solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 90.5% and the purity is 99.4%.
Example 2:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 43.32% (namely, 100g triphenylphosphine oxide waste residue contains 43.32g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding sulfuric acid solution until the pH value is 2-5, reacting at 65-80 ℃ for 4 hours under heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing 86.3g of obtained filter cake with 200mL of water, stirring uniformly, then dropwise adding sodium hydroxide solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 88.6%, and the purity is 99.45%.
Example 3:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 47.32% (namely, 100g triphenylphosphine oxide waste residue contains 47.32g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding an acetic acid solution until the pH value is 2-5, reacting for 4 hours at the temperature of 65-80 ℃ in a heat preservation way, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing 96.3g of obtained filter cake with 200mL of water, stirring uniformly, then dropwise adding a potassium carbonate solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 95.5% and the purity is 99.4%.
Example 4:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the triphenylphosphine oxide external standard content in the waste residue which is 57.32% (namely, 100g triphenylphosphine oxide waste residue contains 57.32g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, and dripping formic acid solution until the pH value is 2-5
Reacting for 4 hours at 65-80 ℃ with heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing 96.3g of obtained filter cake with 200mL of water, stirring uniformly, then dropwise adding sodium hydroxide solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 93.5% and the purity is 99.5%.
Example 5:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 59.26% (namely, 100g triphenylphosphine oxide waste residue contains 59.26g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding an acetic acid solution until the pH value is 2-5, reacting at 65-80 ℃ for 4 hours under heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing 97.4g of obtained filter cake with 200mL of water, stirring uniformly, then dropwise adding sodium hydroxide solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 96.2%, and the purity is 99.5%.
Example 6:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 57.37% (namely, 100g triphenylphosphine oxide waste residue contains 57.37g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding an acetic acid solution until the pH value is 2-5, reacting at 65-80 ℃ for 4 hours under heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing the obtained 94.4g of filter cake with 200mL of water, stirring uniformly, then dropwise adding sodium hydroxide solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 95.8%, and the purity is 99.6%.
Example 7:
Sampling and detecting 100g triphenylphosphine oxide waste residue to obtain the external standard content of triphenylphosphine oxide in the waste residue as 56.35% (namely, 100g triphenylphosphine oxide waste residue contains 56.35g triphenylphosphine oxide); mixing the obtained waste residue with 200g of water, dropwise adding an acetic acid solution until the pH value is 2-5, reacting at 65-80 ℃ for 4 hours under heat preservation, and cooling to 25-40 ℃ to obtain a primary solid-liquid mixture; filtering the primary solid-liquid mixture, mixing the obtained 95.7g filter cake with 200mL water, stirring uniformly, then dropwise adding sodium hydroxide solution into the mixture until the pH value is 9-11, and stirring at room temperature for 30min to obtain a secondary solid-liquid mixture; and (3) carrying out suction filtration on the obtained secondary solid-liquid mixture, mixing the obtained filter cake with 200mL of water, pulping for 30min at the rotating speed of 200rpm, and carrying out suction filtration on the obtained filter cake, wherein the obtained filter cake is triphenylphosphine oxide. In the embodiment, the recovery rate of triphenylphosphine oxide in the triphenylphosphine oxide waste residue is 96.9% and the purity is 99.5%.
The method for recycling the triphenylphosphine oxide has the advantages of simple process steps, mild reaction conditions, short production period, high raw material conversion rate and low cost, and greatly reduces labor operation and energy consumption; the invention has high conversion rate of raw materials, good quality of synthesized products, high yield and convenient post-treatment, and is suitable for industrial production.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The method for recovering triphenylphosphine oxide is characterized by comprising the following steps:
Mixing triphenylphosphine oxide waste residue with water, and mixing the obtained waste residue liquid with acid for reaction to obtain a primary solid-liquid mixture;
mixing solid matters obtained by solid-liquid separation of the primary solid-liquid mixture with water, regulating the pH value of a mixed system to 9-11 by alkali, and reacting to obtain a secondary solid-liquid mixture;
solid phase obtained by solid-liquid separation of the secondary solid-liquid mixture, namely the triphenylphosphine oxide;
the acid is acetic acid, hydrochloric acid, acetic acid, sulfuric acid and formic acid, and the alkali is sodium hydroxide and sodium bicarbonate.
2. The recycling method according to claim 1, comprising the steps of: mixing triphenylphosphine oxide waste residue with water, mixing the obtained waste residue liquid with acetic acid, adjusting the pH value to 2-5.5, and reacting to obtain a primary solid-liquid mixture; mixing the solid substance obtained by solid-liquid separation of the primary solid-liquid mixture with water, and regulating the pH value of the mixed system to 9-11 by alkali for reaction to obtain a secondary solid-liquid mixture; and carrying out solid-liquid separation on the secondary solid-liquid mixture to obtain a solid phase, namely the triphenylphosphine oxide.
3. The recovery method according to claim 1 or 2, wherein in the recovery method, triphenylphosphine oxide acetic acid complex is formed,
4. The recovery method according to claim 1 or 2, characterized in that the molar ratio of triphenylphosphine oxide to acid in the waste liquid is 1: (0.5-3).
5. The recovery method according to claim 1 or 2, characterized in that the temperature of the acidification reaction is 70-80 ℃.
6. The recovery method according to claim 1 or 2, wherein the acidification reaction time is 4-8 hours.
7. The recovery method according to claim 1 or 2, characterized in that the acidification reaction is followed by a cooling process, the cooling temperature being 25-40 ℃.
8. The recovery method according to claim 1 or 2, wherein the primary recovery rate of triphenylphosphine oxide is not less than 85.5%.
9. The recovery process according to claim 1 or 2, characterized in that the triphenylphosphine oxide has a purity of not less than 98.5%.
10. The recovery method according to claim 1 or 2, wherein the recovered solvent is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311422564.XA CN118063508A (en) | 2023-10-31 | 2023-10-31 | Method for recovering triphenylphosphine oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311422564.XA CN118063508A (en) | 2023-10-31 | 2023-10-31 | Method for recovering triphenylphosphine oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118063508A true CN118063508A (en) | 2024-05-24 |
Family
ID=91096237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311422564.XA Pending CN118063508A (en) | 2023-10-31 | 2023-10-31 | Method for recovering triphenylphosphine oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118063508A (en) |
-
2023
- 2023-10-31 CN CN202311422564.XA patent/CN118063508A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111057848A (en) | Method for extracting lithium from lithium-containing solution by solvent extraction | |
| CN110078099B (en) | Method for preparing lithium carbonate from lepidolite leaching purification solution | |
| JP6926010B2 (en) | Method for producing lithium hydroxide | |
| CN111548323B (en) | Recovery method of aminothiazoly loximate | |
| CN115947486A (en) | Desulfurization waste liquid recycling treatment process and system | |
| CN111908510B (en) | Preparation method of high-purity manganese sulfate | |
| CN114988380A (en) | Method for producing food-grade monopotassium phosphate and co-producing high-purity gypsum by using feed-grade calcium hydrophosphate | |
| CN108726569B (en) | Preparation method of silver hexafluoroantimonate | |
| CN112409409B (en) | Recovery method of triphenylphosphine oxide | |
| CN118063508A (en) | Method for recovering triphenylphosphine oxide | |
| CN110803714A (en) | Method for producing vanadium pentoxide by vanadium-containing solution | |
| CN114163389A (en) | Preparation process of 2-methyl-4-amino-5-aminomethyl pyrimidine and methyl formate | |
| CN110467537B (en) | Preparation process of L-p-hydroxyphenylglycine | |
| CN112390266A (en) | Boric acid composite extracting agent and method for recovering boric acid, magnesium and lithium from salt lake old brine | |
| CN1086178C (en) | Process for preparing potassium sulfate by using potassium chloride and aminium sulfate | |
| CN112897600A (en) | Preparation method of tetraamminepalladium sulfate (II) | |
| CN111204779A (en) | Fused salt production method for co-producing high-purity magnesium hydroxide, magnesium carbonate and nitrogen-potassium fertilizer | |
| CN110697772B (en) | Method for removing trace antimony oxide in crude bismuth oxide | |
| CN114959306B (en) | Method for recycling lithium from lithium precipitation mother liquor by closed cycle method | |
| WO2024082156A1 (en) | Method for preparing sucralose crude product by using alcohol-water alkaline hydrolysis system | |
| CN114736118B (en) | Method for separating 3-methoxy-4-hydroxy mandelic acid and preparing high-purity product thereof | |
| CN115029557B (en) | Method for treating copper sulfate mother liquor with high iron content | |
| CN115894553B (en) | Method for separating and purifying glufosinate | |
| CN113149884B (en) | Method for preparing 2, 4-dimethylpyrrole-3, 5-diformate in low-cost clean mode | |
| CN111876608B (en) | Comprehensive soot recovery method based on chloride leaching |
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 |