RU2077511C1 - Method for processing spent copper-ammonia liquor of copper monoxide acetate - Google Patents

Abstract

FIELD: treatment of effluents resulting from synthetic rubber production. SUBSTANCE: copper is precipitated from spent copper-ammonia liquor of copper monoxide acetate using mixture of alkali metal hydroxide, or carbonate, or bicarbonate added to liquor in weight ratio from 1:100 to 100:1, or using waste residue resulting from air cleaning from carbon dioxide gas during production of nitrogen and oxygen using alkali. Sediment thus-precipitated is separated, washed, degassed, while mother Liquor is mixed with washing water and subjected to distillation to recover ammonia and acetic acid. Residual copper is extracted by two-step process on solid sorbent. Method can be used for processing spent copper-ammonia liquor of copper monoxide acetate used to clean diolefins from olefins by chemosorption technique. EFFECT: improved efficiency. 6 tbl

Description

 The invention relates to wastewater treatment technology in the production of synthetic rubbers, in particular, to methods for processing waste waste copper-ammonia solution of copper oxide acetate (MAR), used for the purification of diolefins from olefins by chemisorption.

Closest to the proposed method is a method in which after deposition of copper with sodium hydroxide in the form of hydrates of oxide of oxide and copper oxide, it is then restored at a temperature of 350-400 ^o C, and the final post-treatment of residual amounts of copper is carried out on KU-1 cation exchanger.

 The disadvantage of this method is the insufficient depth of wastewater treatment at high cost to bring the precipitated product to a socially beneficial state.

The objective of the proposed method is the ability to:
1) receive a blue precipitate of basic copper carbonates, which can be used as a pigment in the paint and varnish industry and construction;
2) to utilize the waste (alkali, soda, oil) generated during air purification in nitrogen-oxygen production;
3) eliminate the formation of by-products, and purify the water completely and use it in the water circulation of the enterprise;
4) to conduct the process at low energy costs (it is not necessary to heat the product to 400 ^o C).

The solution to this problem is achieved by performing the following operations:
1) The precipitation of basic copper carbonates by neutralizing MAP (composition see Table 1) with solutions of KOH, NaOH, Na ₂ CO ₃ or NaHCO ₃ or soda-alkaline waste generated during the purification of air from CO ₂ in the production of nitrogen and oxygen (composition cm table 2).

 2. The mother liquor (composition see table. 3) is drained, and the precipitate is washed with water from ammonia and acetic acid, the washings are added to the mother liquor.

 3. The precipitate (pigment paste) is degassed and dried.

 4. The mother liquor and washings are degassed, impurity vapors are returned to the MAP production, and a small amount (0.01% by weight) of the precipitate and copper ions are trapped on ion-exchange resins or adsorbent.

 5. Copper-free water is used in the water circulation system or for other industrial purposes.

The proposed method is illustrated by the following examples:
Example 1

 Obtaining basic copper carbonates.

 200 ml (203.74 g) of MAP with a total copper content of 24.4 g / l (Table 1) are loaded into a 1-liter porcelain beaker, 6 g of KOH are added in the form of a 20% solution (26 ml) to a medium pH equal to 13, with constant stirring for 15 minutes at room temperature.

 The precipitate of basic copper carbonates formed in this case is separated from the mother liquor by filtration through belting, washed with industrial water in a ratio of 1: 1.5 (26.1 g of precipitate and 39.1 g of water) from ammonia and acetic acid (from 2.2% of the mass ammonia and 2.45% of the mass of acetic acid to 0.05% of the mass and 2.0% of the mass, respectively).

 In the industrial scheme, ammonia and acetic acid are returned to production for the preparation of MAP.

The precipitate in the amount of 26.1 g (with a moisture content of 60% wt) is separated from the wash water, degassed and dried in a vacuum oven at room temperature (20-25 ^o C) and vacuum vacuum (20 mm RT.article) for 3 hours. The precipitate yield of basic copper carbonates is 10.44 g in terms of dry product.

The mother liquor with wash water in an amount of 248 g with a copper content of 0.1% by mass, ammonia 2.0% by mass, acetic acid 1.5% by mass is heated at a temperature of 100 ^o C, blowing air for several minutes (until the smell of ammonia disappears ) As a result, an azeotrope in the amount of 50 g with an ammonia content of 10.5% by mass and acetic acid of 7.5% by mass is returned to production for the preparation of the initial copper-ammonia absorption solution.

 Copper oxide in an amount of 0.2 g, obtained by stripping the mixture of the mother liquor and washing water, precipitates as a black precipitate, which is separated by belting, and copper ions (0.01% of the mass) remaining in the mother liquor are trapped on clinoptiloite to the absence of copper in water.

 Tertiary treatment of the mother liquor from copper ions is carried out on two sequentially working adsorption columns filled with clinoptilolite in an amount of 0.1 l each.

The filtrate transmission rate through the sorbent is 10 h ^-1 , room temperature, dynamic exchange capacity is 500 mg / g. The purified mixture of water (mother liquor and wash water) are used in the water treatment system and production purposes.

 The spent clinoptilolite is dried and milled, and then used as a filler in the manufacture of paints.

 Example 2

 It differs from Example 1 in that, to obtain basic copper carbonates, MAP is taken with a total copper concentration of 176.5 g / l (Table 1), which is diluted with water in a ratio of 1: 4 (40 ml of MAP and 160 ml of water) to a total concentration of copper 35.3 g / l and to 200 ml (206.4 g) of the obtained MAP add 7.8 KOH in the form of a 20% solution (32.5 ml) to a pH of 13.0 with constant stirring for 15 minutes at room temperature.

 The resulting precipitate in an amount of 38.2 g, the mother liquor and wash water go through all stages of processing and purification as in example 1.

 Example 3

It differs from example 1 in that 200 ml (203.74 g (MAP with a total copper content of 24.4 g / l and 112 ml (127.7 g) of alkaline alkaline waste are added to precipitate the basic copper carbonates) formed during the purification of air from CO ₂ in the production of nitrogen and oxygen to a pH of 13.0 with constant stirring for 15 minutes at room temperature.

 The resulting precipitate in an amount of 26.1 g (with a moisture content of 60% by mass), the mother liquor and wash water in an amount of 351.5 g with a copper content of 0.1% by mass, ammonia 2.9% by mass, acetic acid 2.0 % of the mass and wash water go through all stages of processing and purification as in example 1.

 Example 4

 It differs from Example 1 in that 200 ml (203.74 g) of MAP with a total copper content of 24.4 g / l (Table 1) is taken to precipitate the basic copper carbonates and solid alkali is added in an amount of 6 g to a pH of 13 , 0 with constant stirring for 15 minutes at room temperature.

 The resulting precipitate in the amount of 26.1 g of mother liquor and wash water pass through all stages of processing and purification as in example 1.

 Example 5

 It differs from Example 1 in that the precipitate of basic copper carbonates is separated from the mother liquor by settling for 40-60 minutes with a content of the main substance in the precipitate of at least 10% by mass (Table 4), the precipitate in an amount of 104.4 g is washed with running water in a ratio of 1: 1.5 from ammonia and acetic acid.

 The mother liquor and wash water go through all stages of purification as in example 1.

 Example 6

 It differs from previous examples in that the precipitation of basic copper carbonates is carried out under production conditions.

A 300 l spent copper-ammonia solution with a total copper content of 24.4 g / l (example 1) is fed into a device with a capacity of 0.5 m ³ , 168 l of soda-alkaline waste (example 3) is added, which are formed during air purification from carbon dioxide gas in the production of nitrogen and oxygen, to a pH of 13.0, with constant stirring for 15-20 minutes at a temperature of 20-25 ^o C. The resulting reaction mixture is fed into the next apparatus for separation of sediment and mother liquor by settling for 1 hour

 The precipitate of the pigment paste, separated from the mother liquor, is washed with water from impurities of ammonia, acetic acid and copper in a ratio of 1: 1.5. Obtained after washing and filtering on a belting filter, the precipitate of the pigment paste (table 4) in an amount of 39.15 kg has a moisture content of 60% of the mass.

The mother liquor and wash water in an amount of 526 kg with a copper content of 0.1% mass, ammonia 2.9% mass, acetic acid 2.0% mass are stripped at a temperature of 100-120 ^o C, resulting in an azeotrope in the amount of 105 kg with an ammonia content of 10.5% acetic acid, 7.5% of the mass is returned to production for the preparation of the initial absorption copper-ammonia solution.

 0.473 kg of copper oxide obtained by stripping the mixture of the mother liquor and wash water precipitates as a black precipitate, is filtered on a belting filter, and the mother liquor mixture and wash water are sent for purification from copper ions.

Post-treatment is carried out on 2 sequentially working adsorption columns filled with clinoptilolite in an amount of 0.25 m ³ each.

 The filtrate transmission rate through the sorbent is 10 hours, the temperature is room temperature, and the dynamic exchange capacity is 500 mg / g. The purified mixture of water (mother liquor and wash water) are used in the water treatment system and production purposes.

 The spent clinoptilolite is dried, milled and used as a filler in the manufacture of paints.

 The pigment was tested in varnish KCH-1000 TU 38.303-02-12-90 in combination with white pigments: zinc oxide and titanium dioxide (the composition is presented in table 5).

 Table 6 presents the test results of the pigment paste according to TU 38.303-02-67-93 in the formulation of enamel KCH-1000 according to TU.

 Example 7 differs from previous examples in that the resulting precipitate of copper carbonates was used as complex micronutrient fertilizer and Burgundy liquid to protect tomatoes from diseases.

 In order to create conditions for obtaining stable planned crops on developed lands that have sufficient quantities of basic micronutrients such as nitrogen, phosphorus, potassium, calcium, magnesium, etc., it is also necessary to have copper, boron, manganese molybdenum, and other micronutrients in sufficient quantities. in the soil leads to plant diseases such as vertex rot and hollow root crops, chlorotic diseases, and many others. The study of the competing effect of all trace elements on the crop showed that the greatest effect is obtained from the use of copper.

Copper is a trace element of a multifaceted biochemical effect on plant development:
part of many enzymes, increasing their activity;
performs complex functions of oxidative processes for the synthesis of carbohydrates, proteins, vitamins;
participates in the processes of photosynthesis, stabilizes chlorophyll, increases its content;
increases resistance to fungal and bacterial diseases;
enhances the water-holding and water-absorbing ability of plants, increasing their resistance to temperature changes.

 The main component of complex microfertilizer is a precipitate of basic copper carbonates obtained by precipitation of spent MAR (Example 1) with an alkali solution.

 When processing tomato plants, a precipitate of basic copper carbonates (with a moisture content of ≈60% mass) in water was used at a rate of 1.2-1.5 g per 10 l of water. The treatment was carried out with this solution of 20 tomato roots at the rate of 0.5 l per plant, compared with control plants (20 pcs) that were not treated with a precipitate of basic copper carbonates.

 As a result of checking the growth of tomatoes, it was found that tomato plants grew more intensively without diseases with a large increase in fruits and biomass, while control plants had a slightly weaker development, with 10% of the fruit being affected by late blight. Compared to control plants, fruit yield increased by 25%

Claims (1)

1 Method for processing spent copper-ammonia solution of copper oxide acetate used in the chemisorption purification of butadiene, including reagent copper deposition, precipitate separation, subsequent processing of the precipitate and mother liquor with the extraction of residual copper, characterized in that the reagent copper deposition is carried out with an alkaline hydroxide mixture metal and carbonate or bicarbonate of an alkali metal in a mass ratio of from 1 100 to 100 1 or with the waste generated during alkaline cleaning of air from carbon dioxide in the production of nitrogen and oxygen, the treatment of the precipitate is carried out by washing and degassing, and the mother liquor is mixed with washing water and subjected to distillation with the release of ammonia and acetic acid, after which the residual copper is extracted by a two-stage treatment on a solid sorbent.

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