A method for treating waste liquid containing butyl

Abstract

The present application discloses a method for treating waste liquid containing butyl, which belongs to the field of chemical engineering technology. In this method, 1-chlorobutane is converted into n-butanol by an alkaline resin, and n-butyl acetate is hydrolyzed to n-butanol under an alkaline reagent, and then high-purity n-butanol is recovered by extractive distillation. This method enables the efficient recovery of n-butanol from the waste liquid and returns it to the front end as a raw material for input. Moreover, the resin and extractant used in this method can be reused. The treated waste liquid is easy to handle and has low cost. The present application reduces the production cost of preparing glufosinate and reduces environmental pollution, and has high industrial application value.

Description

Technical Field

[0001] This application belongs to the field of chemical engineering technology, and particularly relates to a method for treating butyl-containing waste liquid. Background Art

[0002] In the process of preparing glufosinate using monobutyl methylphosphonate (MPE) as a raw material, when 2-amino-4-(methyl(butoxy)phosphoryl)butanenitrile is hydrolyzed with hydrochloric acid, an equivalent amount of butyl organic waste liquid is generated. This waste liquid is a complex organic layer containing water, n-butyl acetate, n-butanol, and 1-chlorobutane. In addition to the binary azeotropes of organic substances and water, it is also very difficult to separate n-butyl acetate and n-butanol. Therefore, when the separation is difficult and the market demand for 1-chlorobutane is low, the disposal of this organic layer becomes a problem; from the perspective of environmental protection or economy, it is of great significance to convert and recover n-butanol from the above butyl-containing organic waste liquid.

[0003] The butyl-containing organic waste liquid generated in the process of glufosinate preparation has a complex composition and is difficult to separate. Resources such as n-butanol are difficult to recover. Currently, the treatment of the organic layer is basically direct combustion followed by alkali liquor absorption; for the conversion of chlorobutane to n-butanol, the conversion rate is low, and there are also by-products, and the separation difficulty is large; currently, the research on recovering n-butanol from butyl-containing waste liquid only focuses on the conversion of 1-chlorobutane to n-butanol or n-butanol derivatives; in the literature Kumpf, Walter; Martinetz, Dieter, Zeitschrift fur Chemie, 1984, vol. 24, 182-183, 1-chlorobutane is converted to n-butanol in the presence of tributylbenzylammonium chloride, with a yield of 80%, and at the same time, there is also 18% of n-butyraldehyde; in the literature Y. Liu et al., Catalysis Letters, 2017, vol.147, 2764-2771, using an ionic liquid as a catalyst and a usage amount of 30%, 1-chlorobutane is converted to n-butyl acetate, with a yield of 67%. In the literature Yu-Qing et al., Synthetic Communications, 2006, vol.36, 3353-3358, using PEG400 as a catalyst, 1-chlorobutane is converted to n-butyl acetate, with a yield of 89%; in the existing literature on the method of converting 1-chlorobutane to n-butanol or n-butyl acetate, the yield is low, by-products are often accompanied, and an additional separation process is required. Summary of the Invention

[0004] The purpose of the implementation of this application is to provide a method for treating butyl-containing waste liquid, which solves the technical problems that the butyl-containing organic waste liquid cannot be fully utilized, n-butanol is difficult to recover, and the conversion rate is low.

[0005] To achieve the above object, the technical solution adopted by this application is: to provide a method for treating waste liquid containing butyl, which specifically includes the following steps:

[0006] (1) Pass the waste liquid containing butyl into a fixed bed of basic resin, heat and react to convert 1-chlorobutane into n-butanol, and obtain a conversion liquid.

[0007] (2) Pass the conversion liquid into an alkali solution and heat and react to decompose n-butyl acetate to produce n-butanol, obtain a decomposition liquid, add an extractant to the decomposition liquid for extraction to obtain an organic layer; rectify the organic layer to obtain n-butanol and the extractant.

[0008] In one embodiment,

[0009] In step (1), the waste liquid containing butyl is a mixture of 1-chlorobutane, n-butanol, n-butyl acetate and water.

[0010] In one embodiment,

[0011] In step (1), a strongly basic resin is used as the basic resin. Specifically, the quaternary basic resin containing quaternary amine (-NR1R2R3) structure is used as the basic resin, where R1, R2, and R3 are alkyl groups of C1-C12 that do not interfere with each other. More specifically, the basic resin is one or two of AmberLite FPA, DOWRESINEX FPA or AmberLite HPR; the amount of the basic resin contained in the fixed bed is 1 Kg.

[0012] In one embodiment,

[0013] In step (1), the heating temperature is 50-100 °C, and the reaction time is 2-10 h. Preferably, the heating temperature is 80 °C, and the reaction time is 6 h.

[0014] In one embodiment,

[0015] In step (2), the alkali solution is one of calcium oxide aqueous solution, calcium hydroxide aqueous solution, sodium hydroxide aqueous solution or potassium hydroxide solution. The concentration of the alkali solution is 20-50%, and the dosage of calcium oxide, calcium hydroxide, sodium hydroxide or potassium hydroxide is 2.2-3.0 mol / Kg of the waste liquid containing butyl; preferably, the alkali solution is sodium hydroxide, the concentration of the alkali solution is 30%, and the dosage is 2.6 mol / Kg of the waste liquid containing butyl.

[0016] In one embodiment,

[0017] In step (2), the heating temperature is 90-110 °C, and the reaction time is 1-2 h. Preferably, the heating temperature is 100 °C, and the reaction time is 1 h.

[0018] In one embodiment,

[0019] In step (ii), the extractant is an alcohol containing 6 - 10 carbon atoms, specifically 1 - hexanol, 2 - hexanol or isomeric 6 - carbon alcohols, 1 - heptanol, 2 - heptanol or isomeric 7 - carbon alcohols, 1 - octanol, 2 - ethylhexanol or other isomeric 8 - carbon alcohols, 1 - nonanol or other isomeric 9 - carbon alcohols, 1 - decanol or other isomeric 10 - carbon alcohols. The extractant can be one or several of the above 6 - 10 carbon alcohols; further, the extractant is one or several of 1 - heptanol, 2 - heptanol, 1 - octanol, 2 - ethylhexanol or 1 - nonanol. Preferably, the extractant is 1 - octanol.

[0020] In one embodiment,

[0021] In step (ii), the volume ratio of the decomposition liquid to the extractant is 1 : 1 - 2. Preferably, the volume ratio of the decomposition liquid to the extractant is 1 : 2.

[0022] In one embodiment,

[0023] In step (ii), n - butanol is obtained by rectification at 117 - 120 °C.

[0024] In one embodiment,

[0025] In step (ii), the rectified extractant can be recycled.

[0026] The present application provides a method for treating butyl - containing waste liquid. In this technical solution, the pretreatment of the butyl - containing waste liquid does not require prior separation of chlorobutane and other organic substances in the waste liquid, and the process is simple; n - butanol is consumed in the synthesis of MPE. This solution efficiently converts the chlorine - containing organic waste liquid in the glufosinate - ammonium preparation process into utilizable n - butanol, thereby reducing the amount of waste liquid treatment and the consumption of n - butanol raw materials. The alkaline resin used can be re - activated and used through alkali treatment, and the alkali used is also a common industrial alkali. The extractant can also be recycled, greatly reducing the process cost and being suitable for large - scale industrial application; the method reacts under normal pressure and low temperature, with mild reaction conditions and energy saving; the waste liquid after the first - step treatment is sodium chloride waste liquid, which is the most common industrial wastewater and is simple and low - cost to treat. The second - step wastewater is by - product acetate (sodium acetate, potassium acetate or calcium acetate), which can be recycled or sold, extending the industrial chain value; compared with the original waste liquid, the COD value in the wastewater is greatly reduced, and the recovery of butyl - containing waste liquid greatly reduces the degree of environmental pollution; in summary, this method efficiently recovers butanol from the waste liquid and returns it to the front - end as a raw material for input. Moreover, the resin and extractant used in this method can be recycled; the treated waste liquid is simple and low - cost to treat. The present application reduces the production cost of glufosinate - ammonium and reduces environmental pollution, and has high industrial application value. Brief Description of the Drawings

[0027] To more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0028] Figure 1 For the recovery of the n-butanol liquid phase diagram. Specific embodiments

[0029] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application more clearly understood, the present application will be further described in detail. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0030] Example 1

[0031] A method for treating butyl-containing waste liquid

[0032] (1). Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0033] (2). Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The dosage of sodium hydroxide is 2.6 mol. Pass the conversion liquid into the alkali solution, heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Distill the organic layer in a distillation column. Take the fraction at 117 - 120 °C at the top of the distillation column as n-butanol, with a mass of 731.4 g, a content of ≥99%, and a yield of 98.6% (calculated based on the amount of substance of butyl). The bottom discharge of the distillation column is extractant 1-octanol, with a mass of 1.95 kg. The recovered 1-octanol is continued to be used for the extraction of the decomposition liquid.

[0034] Example 2

[0035] (1). Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of DOWRESINEX FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0036] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 723.9 g, a content of ≥99%, and a yield of 97.2% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is the extractant 1-octanol, with a mass of 1.92 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0037] Example 3

[0038] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite HPR basic resin and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0039] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 714.7 g, a content of ≥99%, and a yield of 95.5% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is the extractant 1-octanol, with a mass of 1.87 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0040] Example 4

[0041] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat and react at 50 °C for 10 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0042] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 709.9 g, a content of ≥99%, and a yield of 94.6% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-octanol, with a mass of 1.88 kg. 1-octanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0043] Example 5

[0044] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat and react at 100 °C for 2 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0045] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 702.9 g, a content of ≥99%, and a yield of 93.3% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-octanol, with a mass of 1.93 kg. 1-octanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0046] Example 6

[0047] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0048] (2) Add 192.63 g of calcium hydroxide into water to prepare an alkali solution with a concentration of 30%. The amount of calcium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 721.7 g, a content of ≥99%, and a yield of 96.8% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is the extractant 1-octanol, with a mass of 1.89 kg, and 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0049] Example 7

[0050] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0051] (2) Add 145.89 g of potassium hydroxide into water to prepare an alkali solution with a concentration of 30%. The amount of potassium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 729.3 g, a content of ≥99%, and a yield of 98.2% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is the extractant 1-octanol, with a mass of 1.96 kg, and 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0052] Example 8

[0053] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0054] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 50%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol, obtaining a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Distill the organic layer in a distillation column. Take the fraction at 117 - 120 °C at the top of the distillation column as n-butanol, with a mass of 715.3 g, a content of ≥99%, and a yield of 95.6% (calculated based on the amount of substance of butyl). The bottom discharge of the distillation column is extractant 1-octanol, with a mass of 1.93 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0055] Example 9

[0056] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol, obtaining a conversion liquid.

[0057] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 20%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol, obtaining a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Distill the organic layer in a distillation column. Take the fraction at 117 - 120 °C at the top of the distillation column as n-butanol, with a mass of 728.7 g, a content of ≥99%, and a yield of 98.1% (calculated based on the amount of substance of butyl). The bottom discharge of the distillation column is extractant 1-octanol, with a mass of 1.86 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0058] Example 10

[0059] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol, obtaining a conversion liquid.

[0060] (2) Add 120 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 3.3 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 730.4 g, a content of ≥99%, and a yield of 98.4% (calculated based on the amount of substance of butyl). The bottom product of the rectification column is extractant 1-octanol, with a mass of 1.95 kg. 1-Octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0061] Example 11

[0062] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0063] (2) Add 88 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.2 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 719.6 g, a content of ≥99%, and a yield of 96.4% (calculated based on the amount of substance of butyl). The bottom product of the rectification column is extractant 1-octanol, with a mass of 1.91 kg. 1-Octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0064] Example 12

[0065] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0066] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 90 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 727.7 g, a content of ≥99%, and a yield of 97.9% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-octanol, with a mass of 1.96 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0067] Example 13

[0068] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0069] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 110 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 723.9 g, a content of ≥99%, and a yield of 97.2% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-octanol, with a mass of 1.95 kg. 1-octanol can be recycled and used continuously for the extraction of the decomposition liquid.

[0070] Example 14

[0071] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0072] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 2 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-octanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 728.2 g, a content of ≥99%, and a yield of 98% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-octanol, with a mass of 1.92 kg. 1-octanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0073] Example 15

[0074] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0075] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of extractant 1-heptanol to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 721.2 g, a content of ≥99%, and a yield of 96.7% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is extractant 1-heptanol, with a mass of 1.96 kg. 1-heptanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0076] Example 16

[0077] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin, and heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0078] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 2-ethylhexanol to the decomposition liquid for extraction to obtain an organic layer. Distill the organic layer in a distillation column. Take the fraction at 117 - 120 °C at the top of the distillation column as n-butanol, with a mass of 703.9 g, a content of ≥99%, and a yield of 93.5% (calculated based on the amount of substance of butyl). The bottom discharge of the distillation column is the extractant 2-ethylhexanol, with a mass of 1.97 kg. The 2-ethylhexanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0079] Example 17

[0080] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 1 kg of AmberLite FPA basic resin and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0081] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat it at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extractant 1-nonanol to the decomposition liquid for extraction to obtain an organic layer. Distill the organic layer in a distillation column. Take the fraction at 117 - 120 °C at the top of the distillation column as n-butanol, with a mass of 710.9 g, a content of ≥99%, and a yield of 94.8% (calculated based on the amount of substance of butyl). The bottom discharge of the distillation column is the extractant 1-nonanol, with a mass of 1.99 kg. The 1-nonanol can be recycled and continue to be used for the extraction of the decomposition liquid.

[0082] Example 18

[0083] (1) Pass 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate, and water into a fixed bed containing 500 g of AmberLite FPA and 500 g of DOWRESINEX FPA basic resin and heat it at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid.

[0084] (2) Add 104 g of sodium hydroxide to water to prepare an alkali solution with a concentration of 30%. The amount of sodium hydroxide used is 2.6 mol. Pass the conversion liquid into the alkali solution and heat and react at 100 °C for 1 h to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add 2 kg of the extraction agent 1-heptanol and 2-ethylhexanol (1:1) to the decomposition liquid for extraction to obtain an organic layer. Rectify the organic layer in a rectification column. Take the fraction at 117 - 120 °C at the top of the rectification column as n-butanol, with a mass of 726.6 g, a content of ≥99%, and a yield of 97.7% (calculated based on the amount of substance of butyl). The bottom discharge of the rectification column is the extraction agent 1-heptanol and 2-ethylhexanol (1:1), with a mass of 1.98 kg. The 1-heptanol and 2-ethylhexanol (1:1) can be recycled and continue to be used for the extraction of the decomposition liquid.

[0085] This application provides a method for treating butyl-containing waste liquid, which specifically includes the following steps: Pass the butyl-containing waste liquid through an alkaline resin fixed bed, heat and react to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; Pass the conversion liquid into an alkali solution and heat and react to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid. Add an extraction agent to the decomposition liquid for extraction to obtain an organic layer; Rectify the organic layer to obtain n-butanol and an extraction agent; In this technical solution, the pretreatment of the butyl-containing waste liquid does not require prior separation of 1-chlorobutane and other organic substances in the waste liquid, and the process is simple; n-butanol is consumed in the synthesis of MPE. This solution efficiently converts the chlorine-containing organic waste liquid in the preparation process of glufosinate-ammonium into utilizable n-butanol, thereby reducing the amount of waste liquid treatment and the consumption of n-butanol raw materials. The alkaline resin used can be reactivated and reused through alkali treatment, and the alkali used is also a common industrial alkali. The extraction agent can also be recycled, greatly reducing the process cost and being suitable for large-scale industrial applications; This method reacts under normal pressure and low temperature, with mild reaction conditions and energy savings; The waste liquid after the first step of treatment is sodium chloride waste liquid, which is the most common industrial wastewater and is simple and low-cost to treat. The waste water in the second step is by-product acetate (sodium acetate, potassium acetate or calcium acetate), which can be recycled or sold to extend the industrial chain value; Compared with the original waste liquid, the COD value in the waste water is greatly reduced, and the recovery of butyl-containing waste liquid greatly reduces the degree of environmental pollution; In summary, this method efficiently recovers n-butanol from the waste liquid and returns it to the front end as a raw material input. Moreover, the resin and extraction agent used in this method can be recycled; The treated waste liquid is simple and low-cost to treat. This application reduces the production cost of preparing glufosinate-ammonium, reduces environmental pollution, and has high industrial application value.

[0086] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present application, "a plurality of" means two or more unless otherwise specifically defined.

[0087] The foregoing is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present application shall be included within the protection scope of the present application.

Claims

1. A method for treating butyl-containing waste liquid, characterized in that: The specific steps include: (i) passing the butyl-containing waste liquid into an alkaline resin fixed bed, heating the reaction, converting 1-chlorobutane into n-butanol, and obtaining a conversion liquid; (ii) passing the conversion liquid into an alkaline solution for heating reaction to decompose n-butyl acetate into n-butanol to obtain a decomposition liquid, adding an extractant to the decomposition liquid for extraction to obtain an organic layer; and distilling the organic layer to obtain n-butanol and the extractant; The butyl-containing waste liquid in step (i) is a mixture of 1-chlorobutane, n-butanol, n-butyl acetate and water; The extractant in step (ii) is one or more of 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol or 1-nonanol.

2. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: In step (i), the alkaline resin is one or two of AmberLite FPA, DOWRESINEX FPA or AmberLite HPR.

3. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The heating temperature in step (i) is 50-100°C and the reaction time is 2-10 h.

4. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: In step (ii), the alkali solution is one of a calcium oxide aqueous solution, a calcium hydroxide aqueous solution, a sodium hydroxide aqueous solution or a potassium hydroxide solution, the concentration of the alkali solution is 20-50%, and the amount of the calcium oxide, calcium hydroxide, sodium hydroxide or potassium hydroxide is 2.2-3.0 mol / Kg of butyl-containing waste liquid.

5. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The heating temperature in step (ii) is 90-110°C and the reaction time is 1-2 h.

6. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: In step (ii), the volume ratio of the decomposition liquid to the extraction agent is 1:1-2.

7. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The n-butanol in step (ii) is obtained by distillation at 117-120°C.

8. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The extractant distilled out in step (ii) is recycled.

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