Treatment method of butyl-containing waste liquid

Abstract

The invention discloses a butyl-containing waste liquid treatment method, and belongs to the technical field of chemical engineering, the method comprises the following steps: converting 1-chlorobutane into n-butyl alcohol through alkaline resin, hydrolyzing n-butyl acetate in an alkaline reagent to obtain n-butyl alcohol, and then recovering high-purity n-butyl alcohol through extractive distillation; according to the method, the n-butyl alcohol is efficiently recovered from the waste liquid and returns to the front end again to serve as a raw material to be input, and the resin and the extraction agent used in the method can be recycled; and the treated waste liquid is simple to treat and low in cost, so that the production cost of preparing glufosinate-ammonium is reduced, the pollution to the environment is reduced, and the method has very high industrial application value.

Description

Technical Field

[0001] The present application belongs to the field of chemical technology, and in particular relates to a method for treating butyl-containing waste liquid. Background Art

[0002] In the process of preparing glufosinate using methylphosphonite (MPE) as raw material, when 2-amino-4-(methyl(butoxy)phosphonyl)butyronitrile is hydrolyzed with hydrochloric acid, an equivalent amount of butyl organic waste liquid is produced. The waste liquid is a complex organic layer containing water, n-butyl acetate, n-butanol and 1-chlorobutane. In addition to the azeotropic reaction of organic matter and water, n-butyl acetate and n-butanol are also difficult to separate. Therefore, when separation is difficult and the market demand for 1-chlorobutane is low, the disposal of the organic layer becomes a problem. From the perspective of environmental protection or economy, it is of great significance to convert and recover butanol from the above butyl-containing organic waste liquid.

[0003] The butyl-containing organic waste liquid generated during the preparation process of glufosinate ammonium has complex components and is difficult to separate. Resources such as butanol are difficult to recover. At present, the treatment of the organic layer is basically direct combustion and then absorption by alkali solution. For the conversion of chlorobutane to butanol, the conversion rate is low, and there are by-products, which are difficult to separate. At present, the research on the recovery of butanol from butyl-containing waste liquid only focuses on the conversion of 1-chlorobutane into 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 into n-butanol in the presence of tributyl chloroaniline, with a yield of 80%, and 18% of n-butyraldehyde. In the literature Y.Liu et al., Catalysis Letters, 2017, vol.147,2764-2771, ionic liquid is used as a catalyst, 30 % usage, 1-chlorobutane was converted into n-butyl acetate with a yield of 67%. The literature Yu-Qing et al., Synthetic Communicationsw, 2006, vol.36, 3353-3358 used PEG400 as a catalyst to convert 1-chlorobutane into n-butyl acetate with a yield of 89%; in the existing literature, the method of converting 1-chlorobutane into n-butanol or n-butyl acetate has a low yield, is often accompanied by by-products, and requires an additional separation process. 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 butyl-containing organic waste liquid cannot be fully utilized, butanol is difficult to recover, and the conversion rate is low.

[0005] To achieve the above purpose, the technical solution adopted in this application is: to provide a method for treating butyl-containing waste liquid, which specifically includes the following steps: (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, decomposing 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 an extractant.

[0006] In one embodiment, The butyl-containing waste liquid in step (i) is a mixture of 1-chlorobutane, n-butanol, n-butyl acetate and water.

[0007] In one embodiment, Step (i) The alkaline resin uses a strong alkaline resin, specifically a quaternary alkaline resin containing a quaternary amine (-NR1R2R3) structure, wherein R1, R2, and R3 are C1-C12 alkyl groups that do not interfere with each other, and more specifically, the alkaline resin is one or two of AmberLite FPA, DOWRESINEX FPA, or AmberLite HPR; the amount of the alkaline resin contained in the fixed bed is 1 Kg.

[0008] In one embodiment, In step (i), 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.

[0009] In one embodiment, 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 the butyl-containing waste liquid; preferably, the alkali solution is sodium hydroxide, the concentration of the alkali solution is 30%, and the amount is 2.6 mol / Kg of the butyl-containing waste liquid.

[0010] In one embodiment, In step (ii), 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.

[0011] In one embodiment, The extractant in step (ii) 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-decantol or other isomeric 10-carbon alcohols, and the extractant may be one or more of the above 6-10 carbon alcohols; further, the extractant is one or more of 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol or 1-nonanol, preferably, the extractant is 1-octanol.

[0012] In one embodiment, In step (ii), the volume ratio of the decomposition liquid to the extraction agent is 1:1-2, preferably, the volume ratio of the decomposition liquid to the extraction agent is 1:2.

[0013] In one embodiment, Step (ii) n-butanol is obtained by distillation at 117-120°C.

[0014] In one embodiment, The extractant distilled from step (ii) can be recycled.

[0015] The present application provides a method for treating butyl-containing waste liquid. In the present technical scheme, the pretreatment of butyl-containing waste liquid does not require the separation of chlorobutane and other organic matter in the waste liquid in advance, and the process is simple; n-butanol needs to be consumed when synthesizing MPE, and the present scheme efficiently converts the chlorine-containing organic waste liquid in the preparation process of glufosinate ammonium into usable n-butanol, thereby reducing the amount of waste liquid to be treated and the amount of n-butanol raw material consumption, and the alkaline resin used can be reactivated and used by alkaline liquid treatment, and the alkali used is also a common industrial alkali, and the extractant can also be recycled, which greatly reduces the process cost and is suitable for large-scale industrial application; the method reacts at normal pressure and low temperature, the reaction conditions are mild, and energy is saved; the first step The treated waste liquid is sodium chloride waste liquid, which is the most common industrial waste water, and the treatment is simple and low in cost. The waste water from the second step is by-product acetate (sodium acetate, potassium acetate or calcium acetate), which can be recycled or sold, extending the value of the industrial chain; compared with the original waste liquid, the COD value in the waste water is greatly reduced, and the recovery of butyl waste liquid greatly reduces the degree of pollution to the environment; in summary, the method enables butanol to be efficiently recovered from the waste liquid and returned to the front end as a raw material input, and the resin and extractant used in the method can be recycled; the treated waste liquid is simple to treat and low in cost. The present application reduces the production cost of preparing glufosinate ammonium, reduces pollution to the environment, and has high industrial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0017] Figure 1 Liquid phase diagram for recovering n-butanol. DETAILED DESCRIPTION

[0018] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clear, the present application is 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.

[0019] Example 1 A method for treating butyl-containing waste liquid (i) Pass 1 kg of butyl waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water into a fixed bed containing 1 kg of AmberLite FPA alkaline resin, and heat the reaction at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to prepare an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and prepare a decomposition solution, add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 731.4 g, a content of ≥99%, and a yield of 98.6% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.95 kg, and the 1-octanol is recovered and continued to be used for the extraction of the decomposition solution.

[0020] Example 2 (i) Pass 1 kg of butyl waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water into a fixed bed containing 1 kg of DOWRESINEX FPA alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 723.9 g, a content of ≥99%, and a yield of 97.2% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.92 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0021] Example 3 (i) 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water is passed into a fixed bed containing 1 kg of AmberLite HPR alkaline resin, and heated at 80°C for 6 hours to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 714.7 g, a content of ≥99%, and a yield of 95.5% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.87 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0022] Example 4 (i) Pass 1 kg of butyl waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water into a fixed bed containing 1 kg of AmberLite FPA alkaline resin, and heat the reaction at 50 °C for 10 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution. Add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 709.9 g, a content of ≥99%, and a yield of 94.6% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.88 kg. The 1-octanol can be recovered and continued to be used for the extraction of the decomposition solution.

[0023] Example 5 (i) Pass 1 kg of butyl waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water into a fixed bed containing 1 kg of AmberLite FPA alkaline resin, heat and react at 100 °C for 2 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 702.9 g, a content of ≥99%, and a yield of 93.3% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.93 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0024] Example 6 (i) 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 alkaline resin, heat and react at 80°C for 6 hours to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 192.63 g of calcium hydroxide to water to prepare an alkaline solution with a concentration of 30%, and the amount of calcium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and prepare a decomposition solution, add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 721.7 g, a content of ≥99%, and a yield of 96.8% (based on the amount of butyl substance); the bottom discharge of the distillation tower is the extractant 1-octanol, with a mass of 1.89 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0025] Example 7 (i) 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 alkaline resin, heat and react at 80°C for 6 hours to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 145.89 g of potassium hydroxide to water to prepare an alkaline solution with a concentration of 30%, and the amount of potassium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and prepare a decomposition solution, add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 729.3 g, a content of ≥99%, and a yield of 98.2% (calculated as the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.96 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0026] Example 8 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 50%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution. Add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 715.3 g, a content of ≥99%, and a yield of 95.6% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.93 kg. The 1-octanol can be recovered and continued to be used for the extraction of the decomposition solution.

[0027] Example 9 (i) 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 alkaline resin, heat and react at 80°C for 6 hours to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 20%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 728.7 g, a content of ≥99%, and a yield of 98.1% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.86 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0028] Example 10 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 120 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 3.3 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 730.4 g, a content of ≥99%, and a yield of 98.4% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.95 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0029] Embodiment 11 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 88 g of sodium hydroxide into water to prepare an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.2 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and prepare a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 719.6 g, a content of ≥99%, and a yield of 96.4% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.91 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0030] Example 12 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 90°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 727.7 g, a content of ≥99%, and a yield of 97.9% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.96 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition solution.

[0031] Example 13 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide into water to prepare an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion liquid into the alkaline solution, heat and react at 110°C for 1 h, decompose n-butyl acetate into n-butanol, and prepare 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 tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 723.9 g, a content of ≥99%, and a yield of 97.2% (calculated as the amount of butyl substance); the bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.95 kg, and the 1-octanol can be recovered and further used for the extraction of the decomposition liquid.

[0032] Embodiment 14 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 2 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution. Add 2 kg of extractant 1-octanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 728.2 g, a content of ≥99%, and a yield of 98% (based on the amount of butyl substance). The bottom of the distillation tower is the extractant 1-octanol, with a mass of 1.92 kg. The 1-octanol can be recovered and continued to be used for the extraction of the decomposition solution.

[0033] Embodiment 15 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 1-heptanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 721.2 g, a content of ≥99%, and a yield of 96.7% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 1-heptanol, with a mass of 1.96 kg, and the 1-heptanol can be recovered and further used for the extraction of the decomposition solution.

[0034] Example 16 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution; add 2 kg of extractant 2-ethylhexanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 703.9 g, a content of ≥99%, and a yield of 93.5% (based on the amount of butyl substance); the bottom of the distillation tower is the extractant 2-ethylhexanol, with a mass of 1.97 kg. The 2-ethylhexanol can be recovered and continued to be used for the extraction of the decomposition solution.

[0035] Embodiment 17 (i) 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 alkaline resin, heat and react at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide into water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100°C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution. Add 2 kg of extractant 1-nonanol to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120°C component taken from the top of the distillation tower is n-butanol, with a mass of 710.9 g, a content of ≥99%, and a yield of 94.8% (based on the amount of butyl substance). The bottom of the distillation tower is the extractant 1-nonanol, with a mass of 1.99 kg. The 1-nonanol can be recovered and continued to be used for the extraction of the decomposition solution.

[0036] Embodiment 18 (i) 1 kg of butyl-containing waste liquid containing 1-chlorobutane, n-butanol, n-butyl acetate and water was passed into a fixed bed of alkaline resin containing 500 g of AmberLite FPA and 500 g of DOWRESINEX FPA, and heated at 80 °C for 6 h to convert 1-chlorobutane into n-butanol to obtain a conversion liquid; (ii) Add 104 g of sodium hydroxide to water to obtain an alkaline solution with a concentration of 30%, and the amount of sodium hydroxide used is 2.6 mol; pass the conversion solution into the alkaline solution, heat and react at 100 ° C for 1 h, decompose n-butyl acetate into n-butanol, and obtain a decomposition solution. Add 2 kg of extractants 1-heptanol and 2-ethylhexanol (1: 1) to the decomposition solution for extraction to obtain an organic layer; distill the organic layer in a distillation tower, and the 117-120 ° C component taken from the top of the distillation tower is n-butanol, with a mass of 726.6 g, a content of ≥99%, and a yield of 97.7% (based on the amount of butyl substances). The bottom of the distillation tower is the extractants 1-heptanol and 2-ethylhexanol (1: 1), with a mass of 1.98 kg. 1-heptanol and 2-ethylhexanol (1: 1) can be recovered and continued to be used for extraction of the decomposition solution.

[0037] The present application provides a method for treating butyl-containing waste liquid, which specifically comprises the following steps: 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; passing the conversion liquid into an alkaline solution, heating the reaction, decomposing n-butyl acetate into n-butanol, and obtaining a decomposition liquid, adding an extractant to the decomposition liquid for extraction, and obtaining an organic layer; and distilling the organic layer to obtain n-butanol and an extractant. In the present technical scheme, the pretreatment of the butyl-containing waste liquid does not require the pre-separation of 1-chlorobutane and other organic matter in the waste liquid, and the process is simple. n-butanol needs to be consumed when synthesizing MPE. In the present scheme, the chlorine-containing organic waste liquid in the preparation process of glufosinate ammonium is efficiently converted into usable n-butanol, thereby reducing the amount of waste liquid treated and the consumption of n-butanol raw materials. The alkaline resin used can be reactivated and used by alkaline solution treatment, and the alkali used is also a common industrial alkali. The extractant can also be recycled, which greatly reduces the process cost and is suitable for large-scale industrial applications. The method reacts at normal pressure and low temperature, with mild reaction conditions and energy saving. The waste liquid after the first step of treatment is sodium chloride waste liquid, which is the most common industrial wastewater, simple to treat and low in cost. The waste water in the second step is by-product acetate (sodium acetate, potassium acetate or calcium acetate), which can be recycled or sold, extending the value of the industrial chain. Compared with the original waste liquid, the COD value in the wastewater is greatly reduced, and the recovery of butyl waste liquid greatly reduces the degree of pollution to the environment. In summary, the method enables n-butanol to be efficiently recovered from the waste liquid and returned to the front end as a raw material input, and the resin and extractant used in the method can be recycled. The treated waste liquid is simple to treat and low in cost. The present application reduces the production cost of preparing glufosinate ammonium and reduces pollution to the environment, and has high industrial application value.

[0038] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0039] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in 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, decomposing 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.

2. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The butyl-containing waste liquid in step (i) is a mixture of 1-chlorobutane, n-butanol, n-butyl acetate and water.

3. 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.

4. 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.

5. 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.

6. 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.

7. The method for treating butyl-containing waste liquid according to claim 1, characterized in that: The extractant in step (ii) is one or more of 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol or 1-nonanol.

8. 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.

9. 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.

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

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