LU103166B1 - Separation and purification process of by-product 2-chlorethyl n-butyl ether in production process of tris(2-butoxyethyl) phosphate - Google Patents

Separation and purification process of by-product 2-chlorethyl n-butyl ether in production process of tris(2-butoxyethyl) phosphate Download PDF

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LU103166B1
LU103166B1 LU103166A LU103166A LU103166B1 LU 103166 B1 LU103166 B1 LU 103166B1 LU 103166 A LU103166 A LU 103166A LU 103166 A LU103166 A LU 103166A LU 103166 B1 LU103166 B1 LU 103166B1
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butyl ether
chloroethyl
washing
butoxy ethanol
separation
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LU103166A
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German (de)
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Yi Wang
Jianfeng Jiang
Rui Xu
Dixing CHENG
Fubing Wang
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Zhejiang Wansheng Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • 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
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

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Abstract

Disclosed is a separation and purification process of a by-product 2-Chloroethyl n-butyl ether in a production process of Tris(2-butoxyethyl) phosphate, including: adding titanium tetrachloride into recovered 2-Butoxy ethanol containing 2-Chloroethyl n-butyl ether having a concentration greater than or equal to 30%, performing complete dissolving, performing cooling, then dropwise adding excessive phosphoryl trichloride, keeping the temperature for a period of time after dropwise addition, performing continuous heating, completely reacting 2-Butoxy ethanol in the material into butoxy phosphonic dichlorid, performing distillation under reduced pressure, separating crude 2-Chloroethyl n-butyl ether and a bottom material used for preparing TBEP, adding sodium hydroxide and water into the crude 2-Chloroethyl n-butyl ether, performing stirring, alkali washing and washing, performing standing to separate a discharging layer and an alkali washing wastewater layer, adding water into the separated discharging layer, performing stirring and washing, and performing standing to separate finished 2-Chloroethyl n-butyl ether and washing wastewater.

Description

H109WO5LU-PCT23016 30.06.2023
SEPARATION AND PURIFICATION PROCESS OF BY-PRODUCT LU103166 2-CHLOROETHYL N-BUTYL ETHER IN PRODUCTION PROCESS OF
TRIS(2-BUTOXYETHYL) PHOSPHATE
TECHNICAL FIELD
[01] The present invention belongs to the technical field of separation and purification, and particularly relates to a separation and purification process of a by-product 2-Chloroethyl n-butyl ether in a production process of Tris(2-butoxyethyl) phosphate.
BACKGROUND ART
[02] Tris(2-butoxyethyl) phosphate (TBEP) is mainly used for flame retardant and plastification such as Plastic plasticizer, butanediol and flame retardant polyurethane rubber, cellulose, and polyvinyl alcohol, and has good low temperature characteristics.
[03] In the industrial production process of Tris(2-butoxyethyl) phosphate, excessive 2-Butoxy ethanol is usually used to react with phosphorus oxychloride under the catalysis of titanium tetrachloride to produce Tris(2-butoxyethyl) phosphate, which is a by-product of hydrogen chloride. During the reaction process, the side reaction of 2-Butoxy ethanol reacting with hydrogen chloride to produce 2-Chloroethyl n-butyl ether and water is accompanied. The reaction equation is as follows:
[04] HCL + HOC:H40C4H9—>CH;CH,CH:CH:0CH2CH:CL + H,O
[05] Excessive 2-Butoxy ethanol is recovered by distillation under reduced pressure and reused to a reaction process of the next batch of Tris(2-butoxyethyl) phosphate, and 2-Chloroethyl n-butyl ether and 2-Butoxy ethanol are distilled out. Because 2-Chloroethyl n-butyl ether does not react with phosphorus oxychloride, the concentration of 2-Chloroethyl n-butyl ether increases with the continuous recovery and applicatyion of 2-Butoxy ethanol. When the concentration of 2-Chloroethyl n-butyl ether in the recovered 2-Butoxy ethanol increases to greater than 30%, an esterification reaction of
Tris(2-butoxyethyl) phosphate can't reach the end point, and Tris(2-butoxyethyl) phosphate is necessarily completely replaced with 2-Butoxy ethanol to ensure the normal reaction.
Because the treatment of 2-Chloroethyl n-butyl ether was not considered in the design of 1
H109WO5LU-PCT23016 30.06.2023 the production device, further, the hydrogen chloride contained in it was acidic, and the LU103166 discarded and recovered 2-Butoxy ethanol is discharged as wastewater after being treated qualified.
[06] After laboratory verification of discarded and recovered 2-Butoxy ethanol, 2-Chloroethyl n-butyl ether cannot be re-reacted into 2-Butoxy ethanol anew by adding sodium hydroxide solution, and therefor 2-Butoxy ethanol can only be recycled by separating 2-Chloroethyl n-butyl ether from 2-Butoxy ethanol.
[07] After searching the literatures and patents related to the esterification of
Tris(2-butoxyethyl) phosphate, it was found that there were no reports about the recovery and reuse of the by-product 2-Chloroethyl n-butyl ether or how to separate and purify it.
[08] 2-Chloroethyl n-butyl ether has a boiling point of 50°C and a flash point of 46°C.
Through literature retrieval, it is found that there are few patents and literature reports on the synthesis process of 2-Chloroethyl n-butyl ether at home and abroad, and the following process routes can be found:
[09] (1) DES37696; Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 18, p.158
H M
[10] et + HET SASCHA
H H
[11] (2) Harrison, Charles R.; Hodge, Philip; Hunt, Barry J.; Khoshdel, Ezzatollah;
Richardson, Graham Journal of Organic Chemistry, 1983 , vol. 48, # 21 p. 3721 — 3728
[12] Se OH ~ ore”
[13] (3) U.S. patent in 1956: US2768174 i ~
[14] . ry Bg ea Xp eS
[15] Among the above three process routes, the second process route, which uses 2-Butoxy ethanol to react with chloride, is similar to the side reaction in the synthesis of
Tris(2-butoxyethyl) phosphate, but the 2-Chloroethyl n-butyl ether with high purity is usually obtained directly by distillation, which is significantly different from the process 2
H109WO5LU-PCT23016 30.06.2023 route combined with the production process of Tris(2-butoxyethyl) phosphate. LU103166
[16] In the existing industrial production mode of 2-Chloroethyl n-butyl ether, 2-Chloroethyl n-butyl ether with high purity is almost always separated by rectification, and the method is also suitable for separating 2-Chloroethyl n-butyl ether and 2-Butoxy ethanol from the above discarded and recovered 2-Butoxy ethanol, such that the waste can be utilized. However, the separation of 2-Chloroethyl n-butyl ether by rectification requires a large investment in special rectification apparatus, a lot of idle time of apparatus, a large amount of energy consumption for rectification and complicated control. By comprehensive consideration, rectification is not suitable for the existing
Tris(2-butoxyethyl) phosphate production line to be used after corresponding transformation.
SUMMARY
[17] In order to solve the recovery problem of a by-product 2-Chloroethyl n-butyl ether, an objective of the present invention is to provide a separation and purification process of a by-product 2-Chloroethyl n-butyl ether in a production process of Tris(2-butoxyethyl) phosphate.
[18] In order to achieve the above objective, the following technical solution is provided:
[19] The separation and purification process of by-product 2-Chloroethyl n-butyl ether in production process of Tris(2-butoxyethyl) phosphate includes:
[20] 1) adding titanium tetrachloride into recovered 2-Butoxy ethanol containing 2-Chloroethyl n-butyl ether having a concentration greater than or equal to 30%, performing complete dissolving, then cooling a mixed material to 10-15°C, then dropwise adding excessive phosphoryl trichloride, keeping the temperature for 1-2 h after dropwise addition, performing continuous heating to 50-55°C, completely reacting 2-Butoxy ethanol in the material into 2-butoxyethyl phosphonic dichlorid, completely reacting a 2-Butoxy ethanol component in the recovered 2-Butoxy ethanol by excessive phosphorus oxychloride to generate 2-butoxyethyl phosphonic dichlorid with a high boiling point, then separating the 2-Chloroethyl n-butyl ether by simple distillation under reduced pressure, 3
H109WO5LU-PCT23016 30.06.2023 instead of separating 2-Chloroethyl n-butyl ether and 2-Butoxy ethanol by rectification, and LU103166 making the distillation products have high purity; © o
Cl—P—Gl + HO-CH, CH -O-{CH CH, mn (C.H,0C-H,0) —P--01 + HCL
[21] G “
[22] 2) performing distillation under reduced pressure on the material in step 1), separating crude 2-Chloroethyl n-butyl ether and a bottom material,
[23] 3) adding sodium hydroxide and water into the crude 2-Chloroethyl n-butyl ether in step 2), performing stirring, alkali washing and washing, then performing standing to separate a discharging layer and an alkali washing wastewater layer, adding water into the separated discharging layer, performing stirring and washing, and then performing standing to separate finished 2-Chloroethyl n-butyl ether and washing wastewater; and
[24] 4) adding titanium tetrachloride into excessive pure 2-Butoxy ethanol, then controlling the temperature to be 10-15°C, dropwise adding a bottom material solution in step 2), keeping the temperature for 1.5 h after dropwise addition, performing staged heating reaction, then performing distillation under reduced pressure to remove 2-Butoxy ethanol to obtain crude Tris(2-butoxyethyl) phosphate, and then performing alkali washing, washing, distillation and filtration to obtain finished Tris(2-butoxyethyl) phosphate.
[25] Further, in step 1), a mass ratio of total mass of 2-Butoxy ethanol in the recovered 2-Butoxy ethanol to phosphorus oxychloride is 1.3-1.6:1, and addition amount of the titanium tetrachloride accounts for 0.2-0.4% of addition amount of the phosphorus oxychloride; when the proportion of unreacted phosphorus oxychloride to total amount of phosphorus oxychloride added is too small, the content of 2-Butoxy ethanol in distillation fraction of distillation under reduced pressure increases, finally residual amount of 2-Butoxy ethanol in the finished product after 2-Chloroethyl n-butyl ether is washed is too large, and purity of the finished product is unqualified, and when the proportion of the unreacted phosphorus oxychloride to the total amount of the phosphorus oxychloride added is too large, loss of the phosphorus oxychloride is too large, and the crude product is hydrolyzed into sodium phosphate and sodium chloride when the crude product is washed, resulting in unnecessary waste. 4
H109WO5LU-PCT23016 30.06.2023
[26] Further, in step 2), temperature of distillation under reduced pressure is 60-80°C. LU103166
[27] Further, the sodium hydroxide in step 3) is a sodium hydroxide solution, after being added, the sodium hydroxide and the water are stirred at 25-35°C for 20-30 min, and pH is controlled to be 9-10; and the discharging layer is stirred for 15-30 min, and pH is controlled to be 7.
[28] Further, in step 4), a mass ratio of the pure 2-Butoxy ethanol to the titanium tetrachloride is 800-1000:3.
[29] Further, in step 4), a process of staged heating reaction is to perform heating to 30-35°C for 0.5 h, then continuously perform heating to 75-80°C for 0.5 h, and the temperature of distillation under reduced pressure is 160-170°C.
[30] Further, in step 4), specific processes of alkali washing, washing, distillation and filtration are as follows: adding water and sodium hydroxide for alkali washing, performing stirring to separate alkali washing material layers, adding water for washing, performing standing after washing, distilling the upper material layer under reduced pressure, controlling the temperature at 105-110°C, and filtering the lower material layer.
[31] Further, the alkali washing wastewater and the washing wastewater in step 3) and the washing wastewater in step 4) are reused in a washing process of the crude
Tris(2-butoxyethyl) phosphate.
[32] Further, a separation and preparation process is performed at a vacuum condition, and vacuum degree is -0.094 to -0.096 Mpa.
[33] The present invention has the beneficial effects:
[34] 1) The present invention closely combines the production process of
Tris(2-butoxyethyl) phosphate, and utilizes an existing apparatus to centrally treat discarded excessive 2-Butoxy ethanol during production intermission without adding a new apparatus, the 2-Butoxy ethanol in the discarded excessive 2-Butoxy ethanol is reacted into the finished Tris(2-butoxyethyl) phosphate, and then the 2-Chloroethyl n-butyl ether with high purity is obtained by separation.
[35] 2) Usage of rectification separation is avoided, which may greatly reduce energy consumption and an investment cost of the new apparatus.
[36] 3) The wastewater generated from washing of the crude 2-Chloroethyl n-butyl
H109WO5LU-PCT23016 30.06.2023 ether may be reused in a washing link of crude TBEP, and no additional wastewater is LU103166 generated.
[37] 4) Because the discarded and recovered 2-Butoxy ethanol needs to be gradually added into alkaline wastewater, the alkaline wastewater may only be treated by biochemical treatment to be qualified after being diluted to a certain concentration, the wastewater is long in treatment cycle, difficult in treatment and high in cost, and reuse of discarded and recovered 2-Butoxy ethanol reduces a cost of wastewater treatment, which greatly reduces pressure of wastewater treatment.
BRIEF DESCRIPTION OF THE DRAWINGS
[38] FIG 1 1s a flow schematic diagram of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[39] The present invention will be further described below with reference to the accompanying drawings of the description and examples, but the scope of protection of the present invention is not limited to what is described above.
[40] Raw materials used in the following examples:
[41] Recovered 2-Butoxy ethanol: 2-Butoxy ethanol content: 67.61%, 2-Chloroethyl n-butyl ether content: 30%, hydrogen chloride content: 2.24%, and water content: 0.15%;
[42] Phosphorus oxychloride: purity of 99.5%;
[43] Pure 2-Butoxy ethanol: purity of 99.95%, water of 0.05%; and
[44] Titanium tetrachloride: purity of 99.5%.
[45] Example 1
[46] The present example is performed by the process as shown in FIG. 1.
[47] 1) Phosphorus oxychloride was dropwise added in esterification:
[48] 110 g of recovered 2-Butoxy ethanol and 0.3 g of titanium tetrachloride were put into a four-neck flask having a capacity of 500ml, stirring was started, vacuum in the flask was kept at -0.094 Mpa, after the above material was cooled to 10-15°C in an ice bath, 100.3 g of phosphorus oxychloride was slowly dropped into the bottom material, the dropping was completed in about 1.5 h, the vacuum was needed to be controlled at -0.094 6
H109WO5LU-PCT23016 30.06.2023
Mpa, the temperature was needed to be controlled at 15°C during a dropping process, and LU103166 the temperature was kept at 15°C for 1.5 h after dropping was completed;
[49] 2) esterification and heat preservation:
[50] Vacuum degree of a system was kept unchanged, the temperature was raised to 50°C for 1 h, and samples were taken for gas chromatography to detect that there was no residue of 2-Butoxy ethanol, and an intermediate product Al was prepared, and weighed 186.09 g; and
[51] 3) distillation under reduced pressure was performed to separate 2-Chloroethyl n-butyl ether:
[52] The intermediate product Al was moved into a reduced pressure distillation device, the vacuum degree was -0.094 Mpa, system temperature was raised to 75°C, a 2-Chloroethyl n-butyl ether component was distiled off until no fraction was distilled off, distillation was ended to obtain a crude product A2 of 2-Chloroethyl n-butyl ether, which was weighed 35.56 g, the remaining bottom material Bl was weighed 150.53 g, A2 sampling was detected by gas chromatography detection: purity of 2-Chloroethyl n-butyl ether was 92.79%, and purity of residues of 2-Butoxy ethanol was 6.28%, and purity of the rest substances was 0.93% (phosphorus oxychloride and hydrogen chloride).
[53] 4) Post-treatment of crude 2-Chloroethyl n-butyl ether:
[54] The crude product A2 of 2-Chloroethyl n-butyl ether was put into the four-neck flask having a capacity of 500 ml, 15.89 g of water and 1.89 g of sodium hydroxide aqueous solution having a mass concentration of 30% were added, stirring was performed for 20 minutes at room temperature of 25°C, pH was controlled at 9, after temperature keeping, standing was performed for 30 minutes, and an upper material layer A3 was separated for washing; total phosphorus in a separated lower alkali washing wastewater was measured to determine actual content of phosphorus oxychloride in A2, and the total phosphorus was 36 mg/kg by spectrophotometry.
[55] The material layers were added into the four-neck flask, 17.78 g of water was added, stirring was performed at room temperature for 15 minutes, pH was controlled at 7, after temperature keeping, standing was performed for 30 minutes, 34.17 g of finished 2-Chloroethyl n-butyl ether on the upper layer was separated, the content of 2-Chloroethyl 7
H109WO5LU-PCT23016 30.06.2023 n-butyl ether in the finished product was 96.59% by a gas chromatography external LU103166 standard method, residual amount of 2-Butoxy ethanol was 3.26%, water content was 0.15% by Karl Fischer method, and related indexes of the finished product were up to standard;
[56] 5) a residual bottom material B1 of recovered 2-Butoxy ethanol was esterified and dropwise added into pure 2-Butoxy ethanol;
[57] 265 g of pure 2-Butoxy ethanol was put into a four-neck flask having a capacity of 1000 ml, then 0.795 g of titanium tetrachloride was added as a catalyst, vacuum degree was kept at -0.094 Mpa or above, temperature of the bottom material was 15°C, slowly and evenly dropping 152.75 g of B1 was started, a dropping process was about 1 h, after the dropping, the vacuum degree was -0.094 to -0.096 Mpa, and the temperature was 20°C for 1.5h;
[58] 6) Temperature raising and keeping;
[59] The vacuum degree was kept, the temperature was continuously kept for 0.5 h when the temperature was raised to 30°C, then the temperature was kept for 0.5 h when the temperature was raised to 75°C, samples were taken for gas phase detection, residual amount of an intermediate product was less than or equal to 0.1%, and then the reaction was finished to obtain a crude product B2, weighing as 374.87 g;
[60] 7) 2-Butoxy ethanol recovery under reduced pressure:
[61] Under the vacuum degree of -0.094 to -0.096 Mpa, B2 was heated to 160°C and distilled under reduced pressure to recover 2-Butoxy ethanol until no 2-Butoxy ethanol was distilled off, samples were taken, gas phase detection was performed on the crude product, residual amount of 2-Butoxy ethanol was 2.44%, which was qualified, and distillation was finished to obtain 265.37 g of crude phosphate flame retardant TBEP, and 109.5 g of 2-Butoxy ethanol was recovered;
[62] 8) Post-treatment of crude TBEP:
[63] The Crude TBEP B3 was put into the four-neck flask having a capacity 1000 ml, 88.46 g of water and 7.868 g of sodium hydroxide aqueous solution having a mass concentration of 30% were added for alkali washing, stirring was performed at 60°C for 25 minutes, an upper alkali washing material layer was separated and put into the four-neck 8
H109WO5LU-PCT23016 30.06.2023 flask having a capacity of 1000 ml, then 85.5 g of water at 65°C was added, temperature LU103166 was controlled at 65°C, stirring was performed for 15 min, standing was performed for 30 minutes, distillation under reduced pressure was performed on the upper material layer, the vacuum degree was -0.094 Mpa, the highest temperature was controlled at 105°C until no water was distilled off, distillation was finished, 260.54 g of phosphate flame retardant
TBEP was prepared, samples were taken for finished product inspection, and results were as follows: TBEP content was 98.52% (industry standard: > 98.00%) by gas chromatography detection, and water content was 0.05% by Karl Fischer (industry standard: < 0.2%), an acid value was 0.03 KOHmg/g (industry standard: < 0.1 KOHmg/g), and color number was 45 (industry standard: < 60).
[64] Example 2
[65] Other processes are the same as in Example 1, Example 2 only proceeds to step (4), and differences are that:
[66] in step (1), the addition amount of phosphorus oxychloride was changed to 105.06 g, and the addition amount of titanium tetrachloride was changed to 0.315 g.
[67] The crude product A2 of 2-Chloroethyl n-butyl ether distilled in step (3) was weighed as 34.14 g, and gas chromatography detection showed that purity of 2-Chloroethyl n-butyl ether was 96.65%, purity of residues of 2-Butoxy ethanol was 2.18%, and purity of other components (phosphorus oxychloride and hydrogen chloride) was 1.17%. The bottom material B1 of distillation was weighed as 157.46 g.
[68] In step (4), 14.83 g of water and 2.24 g of sodium hydroxide having a mass concentration of 30% were added to alkali washing of A2, 17.07 g of water was added to washing, after A2 was washed, samples were taken, by gas chromatography detection, the content of 2-Chloroethyl n-butyl ether was 98.74%, content of 2-Butoxy ethanol was 1.11%, content of water was 0.15% by Karl Fischer method, and 33.42 g of the finished 2-Chloroethyl n-butyl ether was obtained. The total phosphorus in the separated lower alkali washing wastewater was measured to determine the actual content of phosphorus oxychloride in A2, and the total phosphorus was 837 mg/kg by spectrophotometry.
[69] Example 3
[70] Other processes are the same as in Example 1, and differences are that: 9
H109WO5LU-PCT23016 30.06.2023
[71] in step (1), the addition amount of phosphorus oxychloride was changed to LU103166 106.73 g, and the addition amount of titanium tetrachloride was changed to 0.32 g.
[72] The crude product A2 of 2-Chloroethyl n-butyl ether distilled in step (3) was weighed as 33.81 g, and gas chromatography detection showed that purity of 2-Chloroethyl n-butyl ether was 97.61%, purity of residues of 2-Butoxy ethanol was 1.1%, and purity of other components (phosphorus oxychloride and hydrogen chloride) was 1.29%. The bottom material B1 of distillation was weighed as 159.1 g.
[73] In step (4), 14.49 g of water and 2.42 g of sodium hydroxide aqueous solution having a mass concentration of 30% were added to alkali washing of A2, 16.9 g of water was added to washing, after A2 was washed, samples were taken, by gas chromatography detection, the content of 2-Chloroethyl n-butyl ether was 99.29%, content of 2-Butoxy ethanol was 0.56%, content of water was 0.15% by Karl Fischer method, and 33.24 g of the finished 2-Chloroethyl n-butyl ether was obtained. The total phosphorus in the separated lower alkali washing wastewater was measured to determine the actual content of phosphorus oxychloride in A2, and the total phosphorus was 1246 mg/kg by spectrophotometry.
[74] In step (5), the addition amount of 2-Butoxy ethanol was changed to 289 g, the addition amount of titanium tetrachloride was changed to 0.867 g, and the total amount of
B1 was 159.1 g.
[75] The total amount of crude B2 obtained by the reaction in step (6) was 401.12 g.
[76] In step (7), 118.95 g of 2-Butoxy ethanol was distilled recovered, and 282.17 g of crude TBEP was distilled recovered.
[77] In step (8), 94.06 g of water and 8.27 g of sodium hydroxide were added into alkali washing, 90.93 g of water was added into washing to obtain 277 g of finished TBEP, the content of TBEP detected by gas chromatography in the finished product was 98.52%, and the content of 2-Butoxy ethanol was 1.48%. The acid value was 0.03, water content was 0.053%, and color number was 45.
[78] Example 4
[79] Other processes are the same as in Example 1, an experiment only proceeds to step (4), and differences are that:
H109WO5LU-PCT23016 30.06.2023
[80] in step (1), the addition amount of phosphorus oxychloride was changed to LU103166 108.43 g, and the addition amount of titanium tetrachloride was changed to 0.325 g.
[81] The crude product A2 of 2-Chloroethyl n-butyl ether distilled in step (3) was weighed as 34.03 g, and gas chromatography detection showed that purity of 2-Chloroethyl n-butyl ether was 96.97%, purity of residues of 2-Butoxy ethanol was 0.559%, and purity of other impurities was 2.48%. The bottom material B1 of distillation was weighed as 160.4 g.
[82] In step (4), 12.45 g of water and 4.56 g of sodium hydroxide having a mass concentration of 30% were added to alkali washing of A2, 17.02 g of water was added to washing, after A2 was washed, samples were taken, by gas chromatography detection, the content of 2-Chloroethyl n-butyl ether was 99.57%, content of 2-Butoxy ethanol was 0.28%, and content of water was 0.15% by Karl Fischer method. 33.14 g of the finished 2-Chloroethyl n-butyl ether was obtained. The total phosphorus in the separated lower alkali washing wastewater was measured to determine the actual content of phosphorus oxychloride in A2, and the total phosphorus was 5963 mg/kg by spectrophotometry.
[83] Example 5
[84] Other processes are the same as in Example 1, an experiment only proceeds to step (4), and differences are that:
[85] in step (1), the addition amount of phosphorus oxychloride was changed to 110.2 g, and the addition amount of titanium tetrachloride was changed to 0.33 g.
[86] The crude product A2 of 2-Chloroethyl n-butyl ether distilled in step (3) was weighed as 34.02 g, and gas chromatography detection showed that purity of 2-Chloroethyl n-butyl ether was 97%, no 2-Butoxy ethanol was detected, and purity of other components (phosphorus oxychloride and hydrogen chloride) was 3%. The bottom material B1 of distillation was weighed as 162 g.
[87] In step (4), 11.54 g of water and 5.47 g of sodium hydroxide having a mass concentration of 30% were added to alkali washing of A2, 17.01 g of water was added to washing, after A2 was washed, samples were taken, by gas chromatography detection, the content of 2-Chloroethyl n-butyl ether was 99.85%, content of water was 0.15% by Karl
Fischer method, and 33.05 g of the finished 2-Chloroethyl n-butyl ether was obtained. The 11
H109WO5LU-PCT23016 30.06.2023 total phosphorus in the separated lower alkali washing wastewater was measured to LU103166 determine the actual content of phosphorus oxychloride in A2, and the total phosphorus was 7902 mg/kg by spectrophotometry.
[88] Example 6
[89] Other processes are the same as in Example 1, an experiment only proceeds to step (4), and differences are that:
[90] in step (1), the addition amount of phosphorus oxychloride was changed to 113.78 g, and the addition amount of titanium tetrachloride was changed to 0.34 g.
[91] The crude product A2 of 2-Chloroethyl n-butyl ether distilled in step (3) was weighed as 34.02 g, and gas chromatography detection showed that purity of 2-Chloroethyl n-butyl ether was 96.5%, purity of other impurities (phosphorus oxychloride and hydrogen chloride) was 3.5%, and the bottom material B1 of distillation was weighed as 165.41 g.
[92] In step (4), 10.71g of water and 6.39g of sodium hydroxide having a mass concentration of 30% were added to alkali washing of A2, 17.1g of water was added to washing, after A2 was washed, samples were taken, by gas chromatography detection, the content of 2-Chloroethyl n-butyl ether was 99.85%, content of water was 0.15% by Karl
Fischer method, and 33.05 g of the finished 2-Chloroethyl n-butyl ether was obtained. The total phosphorus in the separated lower alkali washing wastewater was measured to determine the actual content of phosphorus oxychloride in A2, and the total phosphorus was 9772 mg/kg by spectrophotometry.
[93] Example 7
[94] Other processes are the same as in Example 1, an experiment only proceeds to step (4) to complete alkali washing and layering, and differences are that the reduced pressure distillation temperature of Al was changed to 60°C, 24 grams of fractions were collected, after gas chromatography detection, the purity of 2-Chloroethyl n-butyl ether in
A2 was 90.69%, the purity of 2-Butoxy ethanol was 9.3%, the purity of other impurities (phosphorus oxychloride and hydrogen chloride) was 0.012%, and the bottom material B1 of distillation was weighed as 164.3 g. A2 is subjected to alkali washing, and the total phosphorus in an alkali washing water layer is 30 mg/kg.
[95] Example 8 12
H109WO5LU-PCT23016 30.06.2023
[96] Other processes are the same as in Example 1, an experiment only proceeds to LU103166 step (4) to complete alkali washing and layering, and differences are that the reduced pressure distillation temperature of Al was changed to 65°C, 29 grams of fractions were found and collected, after gas chromatography detection, the purity of 2-Chloroethyl n-butyl ether in A2 was 92.3%, the purity of 2-Butoxy ethanol was 7.69%, the purity of other impurities (phosphorus oxychloride and hydrogen chloride) was 0.01%, and the bottom material B1 of distillation was weighed as 159.3 g. A2 is subjected to alkali washing, and the total phosphorus in an alkali washing water layer is 32 mg/kg.
[97] Example 9
[98] Other processes are the same as in Example 1, an experiment only proceeds to step (4) to complete alkali washing and layering, and differences are that the reduced pressure distillation temperature of Al was changed to 70°C, 31 grams of fractions were found and collected, after gas chromatography detection, the purity of 2-Chloroethyl n-butyl ether in A2 was 92.79%, the purity of 2-Butoxy ethanol was 7.2%, the purity of other impurities (phosphorus oxychloride and hydrogen chloride) was 0.01%, and the bottom material B1 of distillation was weighed as 157.3 g. A2 is subjected to alkali washing, and the total phosphorus in an alkali washing water layer is 33 mg/kg.
[99] Example 10
[100] Other processes are the same as in Example 1, an experiment only proceeds to step (4) to complete alkali washing and layering, and differences are that the reduced pressure distillation temperature of Al was changed to 80°C, 35 grams of fractions were found and collected, after gas chromatography detection, the purity of 2-Chloroethyl n-butyl ether in A2 was 91.67%, the purity of 2-Butoxy ethanol was 6.2%, the purity of other impurities (phosphorus oxychloride and hydrogen chloride) was 2.136%, and the bottom material B1 of distillation was weighed as 152.3 g. A2 is subjected to alkali washing, and the total phosphorus in an alkali washing water layer is 8304 mg/kg.
[101] A gas chromatographic detection method used in the experiment:
[102] 1. A gas chromatographic detection apparatus and parameters of an area normalization method in step (2), step (3) and step (6) and an external standard method in step (8): 13
H109WO5LU-PCT23016 30.06.2023
[103] © Detection apparatus and model: Shimadzu gas chromatograph GC-2010Pro | LU103166
[104] © Setting conditions: SPL1 temperature: 280°C
[105] SPL1 pressure: 55.4 KPa
[106] N2 purge flow: 3.0 mL/min
[107] Initial pressure: 653 KPa
[108] Total flow: 17.7 mL/min
[109] Chromatographic column temperature: 100°C
[110] © Standard substance used in the external standard method: triethyl phosphate having a concentration of 99.9% is used as a calibration substance, which is added to samples according to the mass ratio of 10%, and then diluted with methanol at a ratio of 1:10.
[111] 2. Detection method of phosphorus content in step (3): ammonium molybdate spectrophotometry GB 11893-89
[112] 3. Gas chromatography external standard method in step (4):
[113] © Detection apparatus and model: Shimadzu gas chromatograph GC-2010Pro
[114] © Setting conditions: SPL1 temperature: 280°C
[115] SPL1 pressure: 55.4 KPa
[116] N2 purge flow: 3.0 mL/min
[117] Initial pressure: 653 KPa
[118] Total flow: 17.7 mL/min
[119] Chromatographic column temperature: 100°C
[120] D Detection method:
[121] Water content Karl Fischer method apparatus model in step (4) and step (8): 870TitroLine KF;
[122] Acid value detection in step (8): a detection method for acid value of petroleum products, GB 264-83; and
[123] Color number detection in step (8): a detection method for color number of platinum and cobalt refers to GB 3143-1982.
[124] Analysis of experimental results:
[125] In the six experiments from Example 1 to Example 6, the mass of 99.5% of active 14
H109WO5LU-PCT23016 30.06.2023 components of the added phosphorus oxychloride reacts with 2-Butoxy ethanol is 96.75 g, LU103166 and the contents of components are shown in Table 1 below
[126] Table 1 Contents of components in Example 1 to Example 6
Proportion of
Mass of Determinati unreacted effective on of total|2-Butoxy 2-Chloroethyl phosphorus Finished components phosphorus | ethanol in|n-butyl ether oxychloride to 2-Chloroethy
Experiment |of added mg/kg —in|finished in finished the effective 1 n-butyl phosphorus A2 alkali |2-Chloroethyl |2-Chloroethyl components of ether (g) oxychloride washing n-butyl ether |n-butyl ether phosphorus (2) wastewater oxychloride 104.5 7.45% 1.11% 98.74% 33.42 106.2 8.90% 1246 0.56% 99.29% 33.24 107.9 10.33% 5963 0.28% 99.57% 33.14 109.6 11.77% 7902 o 99.85% 33.05 6 113.2 14.54% 9772 o | 99.85% 33.05
[127] 1. Confirmation of phosphorus oxychloride addition conditions:
[128] Analysis:
[129] © Comparing experiments 1 to 6, when the effective components of phosphorus oxychloride exceed the reaction amount by more than 8.90%, the main content of the finished 2-Chloroethyl n-butyl ether exceeds 99%, which reaches a qualified range.
[130] © Considering that a part of excessive phosphorus oxychloride is distilled with the crude 2-Chloroethyl n-butyl ether and reacts in an alkali washing link of crude product
A2 of 2-Chloroethyl n-butyl ether to produce sodium phosphate and sodium chloride. It may be seen from total phosphorus value of A2 alkali washing water from experiment 1 to experiment 6 that the greater the total phosphorus value, the greater the loss of phosphorus oxychloride, resulting in an increase in a material consumption cost.
[131] Cost control and quality are considered comprehensively, the addition amount of
H109WO5LU-PCT23016 30.06.2023 phosphorus oxychloride in experiment 3 is preferably selected as the best addition LU103166 proportion.
[132] 2. Selection of distillation temperature conditions in step (3)
[133] Comparing the mass of distilled products and the content of 2-Chloroethyl n-butyl ether in Example 1, Example 7, Example 8, Example 9 and Example 10, it may be seen that when the distillation temperature of 2-Chloroethyl n-butyl ether is lower than 75°C, more 2-Chloroethyl n-butyl ether is remained in the bottom material, which affects a yield.
[134] Comparing total phosphorus data of alkali washing wastewater in step (4) of
Example 1, Example 7, Example 8, Example 9 and Example 10, it may be seen that phosphorus oxychloride is mostly entrained by distillation before 75°C, and a loss is close; and when the distillation temperature is 80°C, excessive phosphorus oxychloride is distilled off in large quantities because the temperature reaches a boiling point under vacuum, which leads to a significant increase in a phosphorus oxychloride loss.
[135] In Example 1, by controlling the distillation temperature of 75°C, most of 2-Chloroethyl n-butyl ether may be distilled off, and a large amount of phosphorus oxychloride is not entrained and distilled out. The conditions are obtained for distillation vacuum degree between -0.094 MPa and -0.096 Mpa, and when a vacuum effect becomes worse, the optimum temperature should be greater than 75°C. 16

Claims (9)

H109WO5LU-PCT23016 30.06.2023 CLAIMS LU103166 WHAT IS CLAIMED IS:
1. À separation and purification process of a by-product 2-Chloroethyl n-butyl ether in a production process of Tris(2-butoxyethyl) phosphate, comprising: 1) adding titanium tetrachloride into recovered 2-Butoxy ethanol containing 2-Chloroethyl n-butyl ether having a concentration greater than or equal to 30%, performing complete dissolving, then cooling a mixed material to 10-15°C, then dropwise adding excessive phosphoryl trichloride, keeping the temperature for 1-2 h after dropwise addition, performing continuous heating to 50-55°C, and completely reacting 2-Butoxy ethanol in the material into 2-butoxyethyl phosphonic dichlorid, 2) performing distillation under reduced pressure on the material in step 1), separating crude 2-Chloroethyl n-butyl ether and a bottom material; 3) adding sodium hydroxide and water into the crude 2-Chloroethyl n-butyl ether in step 2), performing stirring, alkali washing and washing, then performing standing to separate a discharging layer and an alkali washing wastewater layer, adding water into the separated discharging layer, performing stirring and washing, and then performing standing to separate finished 2-Chloroethyl n-butyl ether and washing wastewater; and 4) adding titanium tetrachloride into excessive pure 2-Butoxy ethanol, then controlling the temperature to be 10-15°C, dropwise adding a bottom material solution in step 2), keeping the temperature for 1.5 h after dropwise addition, performing staged heating reaction, then performing distillation under reduced pressure to remove 2-Butoxy ethanol to obtain crude Tris(2-butoxyethyl) phosphate, and then performing alkali washing, washing, distillation and filtration to obtain finished Tris(2-butoxyethyl) phosphate.
2. The separation and purification process according to claim 1, wherein in step 1), a mass ratio of total mass of 2-Butoxy ethanol in the recovered 2-Butoxy ethanol to phosphorus oxychloride is 1.3-1.6:1, and addition amount of the titanium tetrachloride accounts for 0.2-0.4% of addition amount of the phosphorus oxychloride.
3. The separation and purification process according to claim 1, wherein in step 2), temperature of distillation under reduced pressure is 60-80°C. 1
H109WO5LU-PCT23016 30.06.2023
4. The separation and purification process according to claim 1, wherein the sodium LU103166 hydroxide in step 3) is a sodium hydroxide solution, after being added, the sodium hydroxide and the water are stirred at 25-35°C for 20-30 min, and pH is controlled to be 9-10; and the discharging layer is stirred for 15-30 min, and pH is controlled to be 7.
5. The separation and purification process according to claim 2, wherein in step 4), a mass ratio of the pure 2-Butoxy ethanol to the titanium tetrachloride is 800-1000:3.
6. The separation and purification process according to claim 1, wherein in step 4), a process of staged heating reaction is to perform heating to 30-35°C for 0.5 h, then continuously perform heating to 75-80°C for 0.5 h, and the temperature of distillation under reduced pressure is 160-170°C.
7. The separation and purification process according to claim 1, wherein in step 4), specific processes of alkali washing, washing, distillation and filtration are as follows: adding water and sodium hydroxide for alkali washing, performing stirring to separate alkali washing material layers, adding water for washing, performing standing after washing, distilling the upper material layer under reduced pressure, controlling the temperature at 105-110°C, and filtering the lower material layer.
8. The separation and purification process according to claim 1, wherein the alkali washing wastewater and the washing wastewater in step 3) and the washing wastewater in step 4) are reused in a washing process of the crude Tris(2-butoxyethyl) phosphate.
9. The separation and purification process according to claim 1, wherein a separation and preparation process is performed at a vacuum condition, and vacuum degree is -0.094 to -0.096 Mpa. 2
LU103166A 2022-06-09 2023-06-06 Separation and purification process of by-product 2-chlorethyl n-butyl ether in production process of tris(2-butoxyethyl) phosphate LU103166B1 (en)

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