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A kind of method for separating and recovering oxalic acid from oxalic acid waste liquid

A technology of waste liquid separation and oxalic acid, applied in the separation/purification of carboxylic acid compounds, chemical instruments and methods, alkali metal sulfite/sulfate purification, etc., can solve the problem of high recovery cost, increased production cost and decreased activity and other problems, to achieve the effect of high recycling efficiency, environmental protection and low cost

Inactive Publication Date: 2015-10-28
CENT SOUTH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Using lead sulfate as an intermediate to recycle oxalic acid, the biggest disadvantage is that the waste water from oxalic acid recovery contains lead, which causes environmental pollution
In addition, the activity of lead sulfate gradually decreases with the increase of the number of uses, resulting in low yield of oxalic acid and high production cost
Although the recovery of oxalic acid by the lime-gypsum method solves the problem of heavy metal lead pollution, what is obtained is a mixture of calcium oxalate and calcium sulfate, and the separation and recovery of oxalic acid from the mixture of calcium oxalate and calcium sulfate is complicated, and the recovery rate of oxalic acid is low. High cost and produces a lot of waste water and residue

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] The oil waste pickling wastewater was filtered while it was hot at 80°C to obtain 105kg of mixed filter residue of oxalic acid-sodium oxalate and 2.5m 3 Filtrate containing sodium sulfate. The filtrate is cooled to 5°C, sodium sulfate salt is crystallized, and about 10 kg of sodium sulfate salt crystals and its crystallization mother liquor are obtained by filtration, and the crystallization mother liquor is returned to the oil excrement pickling process. Take 100kg of oxalic acid-sodium oxalate mixed filter residue and put it into 1.5 times the theoretical amount of oxalic acid converted into oxalic acid, add 5mol / L HCl solution, stir at 60°C, absorb the floating superposition oil at rest, cool to 5°C to crystallize for 4h, and let the oxalic acid in it Crystals were precipitated and filtered to obtain oxalic acid crystals and mother liquor of oxalic acid crystals. The obtained oxalic acid crystals were mixed with water at a solid-to-liquid ratio of 1:2g / ml, heated to...

Embodiment 2

[0028] Take 1000 g of the oxalic acid-sodium oxalate mixed filter residue obtained in Example 1, add the oxalic acid crystallization mother liquor obtained in Example 1 at a solid-to-liquid ratio of 1:3 g / ml, and add 2 times the theoretical amount of oxalic acid converted from the mixed filter residue to slowly add 12 mol / L HCl concentrated hydrochloric acid, stir at 85°C, absorb the floating heavy oil in the upper layer, filter and remove the precipitated sodium chloride solid, cool the filtrate to 10°C to crystallize for 2 hours, and let the oxalic acid crystallize out. Filter to obtain oxalic acid crystals and oxalic acid crystallization mother liquor. Add the obtained oxalic acid crystals to the recrystallization mother liquor obtained in Example 1 at a solid-to-liquid ratio of 1:5 g / ml, raise the temperature to 60°C to dissolve the oxalic acid crystals, then cool to 5°C to allow the oxalic acid to recrystallize and precipitate, and filter to obtain recrystallized oxalic a...

Embodiment 3

[0030] Take 500 g of the mixed filter residue of oxalic acid-sodium oxalate salt obtained in Example 1, put it into 5 times the theoretical amount of oxalic acid, add 3mol / L HCl solution, stir at 65 ° C, and absorb the floating superposition oil in the upper layer statically, then filter to remove the precipitated chlorine After the solidification of sodium, the filtrate was cooled to 7°C and crystallized for 5 hours to precipitate the oxalic acid crystals, and filtered to obtain oxalic acid crystals and oxalic acid crystallization mother liquor. Add water to the obtained oxalic acid crystals at a solid-to-liquid ratio of 1:1 g / ml and stir, heat up to 100°C to dissolve the oxalic acid crystals, cool to 15°C to allow oxalic acid to recrystallize and precipitate, and filter to obtain recrystallized oxalic acid and oxalic acid recrystallized mother liquor. After recrystallized oxalic acid is dried, the oxalic acid product with a purity of 99.9% is obtained. After mixing the recry...

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Abstract

The invention relates to a method for separating and recovering oxalic acid from waste oxalic acid liquor. The method comprises the following procedures: separation and recovery of oxalic acid-sodium oxalate salt mixed crystals and sodium sulfate salt crystals, transformation of mixed crystals, refining of oxalic acid and refining of sodium sulfate sodium, and is characterized by comprising the following steps: filtering oilstone pickling waste water during the production process of borneol while being hot, to obtain oxalic acid-sodium oxalate salt mixed crystals, and filtrate containing sodium sulfate salt; cooling and crystalizing the filtrate, and filtering to obtain sodium sulfate salt crystals and crystallized mother liquor; transforming and refining the oxalic acid-sodium oxalate salt mixed crystals to obtain a qualified oxalic acid product; transforming sodium sulfate salt through neutralization and drying to obtain anhydrous sodium sulfate. Valuable constituents in waste water can be effectively separated and recovered, no waste water and waste residues are generated during the whole technological process, the purity of the recovered anhydrous oxalic acid can achieve more than 99.8%, the total recovery rate of oxalic acid in the waste water can achieve more than 99%, so that the method is high in recovery rate, low in cost, environmentally friendly and suitable for industrial application.

Description

technical field [0001] The invention relates to a method for separating and recovering oxalic acid from oxalic acid waste liquid, belonging to the technical field of chemical industry and metallurgy. Background technique [0002] Oxalic acid is the raw material for the production of borneol by turpentine esterification-saponification method. The mixture of sodium oxalate and by-product overlapping oil produced after saponification of oxalic acid ester is commonly known as "oil poop". After the oil feces is washed with sulfuric acid, the heavy oil can be recovered by phase separation. The obtained washing water is an acidic mixed solution of oxalic acid, sodium oxalate and sodium sulfate, which has a high recovery value. The traditional methods for recovering oxalic acid from oil waste washing wastewater are lead sulfate method and lime-gypsum method. Using lead sulfate as an intermediate to recover oxalic acid has the biggest disadvantage that the waste water from oxalic ac...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C51/42C07C51/43C07C55/06C01D3/04C01D5/16
CPCC01D3/04C01D5/16C07C51/42C07C51/487C07C55/06
Inventor 王学文杨洋王明玉
Owner CENT SOUTH UNIV