CN102115405A - Method for preparing pentaerythritol as well as ammonium formate and sodium carbonate - Google Patents

Abstract

The invention provides a method for preparing pentaerythritol as well as ammonium formate and sodium carbonate. The method comprises the following steps: waste liquor generated during the production of pentaerythritol through condensation of formaldehyde and acetaldehyde is distilled under reduced pressure to obtain a saturated pentaerythritol solution, the saturated pentaerythritol solution is then cooled, and pentaerythritol crystals and a filtrate I are obtained through filtering separation; the pentaerythritol crystals are washed, dried and crushed into pentaerythritol products; the filtrate I is distilled under reduced pressure into a saturated sodium formate solution, the saturated sodium formate solution is cooled, and sodium formate crystals are obtained through filtering separation; the sodium formate crystals are dissolved in water and then react with an ammonium carbonate solution to obtain a solution, and then the solution is filtered to obtain a clear filtrate III; the filtrate III is distilled under reduced pressure to obtain a saturated sodium carbonate solution, the temperature of the saturated sodium carbonate solution is reduced to 0 DEG C, and sodium carbonate crystals and a filtrate IV are obtained through filtering separation; the filtrate IV is distilled under reduced pressure to obtain a supersaturated ammonium formate solution, the temperature of the supersaturated ammonium formate solution is reduced to 0 DEG C, and ammonium formate crystals are obtained through filtering separation; and the sodium carbonate crystals and the ammonium formate crystals are respectively washed, dried and crushed into sodium carbonate and ammonium formate products.

Description

A kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash

Technical field

The present invention relates to the organic chemical industry and produce the improvement of tetramethylolmethane gained waste liquid and the technical field of utilization, especially a kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, its raw material is for producing tetramethylolmethane gained waste liquid.

Background technology

Tetramethylolmethane is a kind of organic intermediate of having many uses, and is usually used in coatings industry, is the raw material of alkydpaints, and hardness, glossiness and the weather resistance of paint film are improved; Also be used as the abietinic raw materials such as printing-ink of varnish, colored paint, and can make the coating of flame retardant resistance, siccative oil and aero oil lubricate wet goods.Be that to make the tetramethylolmethane tetranitrate be volatile explosive to raw material with the tetramethylolmethane.The sour fat of tetramethylolmethane fat can be made the softening agent and the stablizer of polyvinyl chloride resin, in addition, also can be used for medicine, agricultural chemicals and lubricated wet goods manufacturing.

Tetramethylolmethane is to be raw material with formaldehyde and acetaldehyde, and condensation makes in the presence of basic catalyst.Be exactly specifically: 37% formaldehyde is under condition of stirring and sodium hydroxide and acetaldehyde, slowly be warming up to 25-32 degree centigrade with steam, keeping this temperature stirred 6-7 hour, the sulfuric acid that adds with mole folding hundred such as sodium hydroxide neutralizes, and the filtrate vapourisation under reduced pressure is concentrated, crystallization, filtration and drying make finished product.

Produce tetramethylolmethane gained waste liquid and come the mother liquor and the washing water of inherent filtration and washing.Contain sodium formiate 25%, tetramethylolmethane 6-8%, other organic substances 15% in the mother liquor.One ton of tetramethylolmethane of every production has 3 cubic metres of crystalline mother solutions to discharge approximately.If by yield 80%, one ton of tetramethylolmethane of then every production is wanted 0.6 ton of by-product sodium formiate.With volume calculation unit be: the sodium formiate volume content is 300-500 (g/L), tetramethylolmethane volume content 50-100 (g/L), and the mother liquor quantity discharged of producing product per ton is the 2-3 ton.

Discharge arbitrarily or abandon if produce tetramethylolmethane gained waste liquid,, also waste raw material, for this reason, be necessary to explore the comprehensive regulation and methods for using them of producing tetramethylolmethane gained waste liquid without influencing environment.

Summary of the invention

Produce tetramethylolmethane with formaldehyde and acetaldehyde condensation, contain sodium formiate 25wt.%, tetramethylolmethane 6-8wt.%, other organic substances 15wt.% in the gained waste liquid.For to its comprehensive regulation and application, the invention provides a kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, its raw material is that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid.This method, formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid through simple processing treatment, make tetramethylolmethane, ammonium formiate and yellow soda ash, make full use of formaldehyde and acetaldehyde condensation and produced the potential value of tetramethylolmethane gained waste liquid, and do not produce secondary pollution, being one turns waste into wealth, economic and practical method.

Technical scheme of the present invention is as follows: a kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, its raw material are that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid, comprise the steps:

Steps A: is the tetramethylolmethane saturated solution with formaldehyde and acetaldehyde condensation production tetramethylolmethane gained waste liquid through underpressure distillation, and postcooling, the tetramethylolmethane crystallization is separated out, and separates after filtration, obtains crystals of pentaerythritol and filtrate one; Filtrate one further underpressure distillation is the sodium formiate saturated solution, and postcooling, the sodium formiate crystallization is separated out, and is separating after filtration, obtains sodium formiate crystal and filtrate two;

Step B: the above-mentioned crystals of pentaerythritol that obtains through washing, dry and pulverizing, is obtained the tetramethylolmethane product;

Step C: the above-mentioned sodium formiate crystal that obtains is water-soluble, it is 2 with the ratio of the molar content of the pure substance of sodium formiate and volatile salt then: the 0.8-1.2 reaction with sal volatile, obtain containing the solution of ammonium formiate and yellow soda ash, after filtration, obtain extremely a spot of filter cake impurity and clarifying filtrate three;

Step D: filtrate three is saturated solution of sodium carbonate through underpressure distillation, is cooled to 0 ℃, and at this moment, the saturation ratio of yellow soda ash is 7.0g, the saturation ratio of ammonium formiate is 102g, and therefore, crystallize sodium carbonate is separated out, and ammonium formiate separates still in solution after filtration, obtains crystals of sodium carbonate and filtrate four; Filtrate four further underpressure distillation are the ammonium formiate supersaturated solution, are cooled to 0 ℃, and at this moment, because the content of yellow soda ash is few in this moment solution, therefore, the ammonium formiate mass crystallization is separated out, and separates after filtration, obtains the ammonium formiate crystal; Crystals of sodium carbonate and ammonium formiate crystal advance washing, dry and pulverizing respectively, thereby obtain yellow soda ash product and ammonium formiate product respectively.

The method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash of the present invention, its chemical equation:

2HCOONa+(NH ₄) ₂CO ₃＝＝＝＝2HCOONH ₄+Na ₂CO ₃

Beneficial effect of the present invention is: the method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash of the present invention, formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid through simple processing treatment, make tetramethylolmethane coproduction ammonium formiate and yellow soda ash, make full use of formaldehyde and acetaldehyde condensation and produced the potential value of tetramethylolmethane gained waste liquid, and do not produce secondary pollution, being one turns waste into wealth, economic and practical method.This method is simple to operate, and facility investment is few, is worthy of popularization.

Embodiment

Embodiment 1: a kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, its raw material are that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid, and wherein, sodium formiate 25wt.%, tetramethylolmethane 7wt.% comprise the steps:

Steps A: formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid 544kg, are the tetramethylolmethane saturated solution through underpressure distillation, and postcooling, the tetramethylolmethane crystallization is separated out, and separates after filtration, obtains crystals of pentaerythritol and filtrate one; Filtrate one further underpressure distillation is the sodium formiate saturated solution, and postcooling, the sodium formiate crystallization is separated out, and is separating after filtration, obtains sodium formiate crystal and filtrate two;

Step B: the above-mentioned crystals of pentaerythritol that obtains through washing, dry and pulverizing, is obtained the tetramethylolmethane product; The quality of the tetramethylolmethane pure substance that it contains is 38.08kg;

Step C: the above-mentioned sodium formiate crystal that obtains is water-soluble, be reaction in 2: 1.2 with the ratio of the molar content of the pure substance of sodium formiate and volatile salt then with sal volatile, obtain containing the solution of ammonium formiate and yellow soda ash, after filtration, obtain extremely a spot of filter cake impurity and clarifying filtrate three;

Step D: filtrate three is saturated solution of sodium carbonate through underpressure distillation, is cooled to 0 ℃, and at this moment, the saturation ratio of yellow soda ash is 7.0g, the saturation ratio of ammonium formiate is 102g, and therefore, crystallize sodium carbonate is separated out, and ammonium formiate separates still in solution after filtration, obtains crystals of sodium carbonate and filtrate four; Filtrate four further underpressure distillation are the ammonium formiate supersaturated solution, are cooled to 0 ℃, and at this moment, because the content of yellow soda ash is few in this moment solution, therefore, the ammonium formiate mass crystallization is separated out, and separates after filtration, obtains the ammonium formiate crystal; Crystals of sodium carbonate and ammonium formiate crystal advance washing, dry and pulverizing respectively, thereby obtain yellow soda ash product and ammonium formiate product respectively; The quality of the pure substance of the yellow soda ash that it contains is 106kg, and the quality of the pure substance of the ammonium formiate that it contains is 126kg.

Embodiment 2:

A kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, its raw material are that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid, and wherein, sodium formiate 25wt.%, tetramethylolmethane 7wt.% comprise the steps:

Steps A: formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid 544kg, are the tetramethylolmethane saturated solution through underpressure distillation, and postcooling, the tetramethylolmethane crystallization is separated out, and separates after filtration, obtains crystals of pentaerythritol and filtrate one; Filtrate one further underpressure distillation is the sodium formiate saturated solution, and postcooling, the sodium formiate crystallization is separated out, and is separating after filtration, obtains sodium formiate crystal and filtrate two;

Step B: the above-mentioned crystals of pentaerythritol that obtains through washing, dry and pulverizing, is obtained the tetramethylolmethane product; The quality of the tetramethylolmethane pure substance that it contains is 38.08kg;

Step C: the above-mentioned sodium formiate crystal that obtains is water-soluble, be reaction in 2: 1 with the ratio of the molar content of the pure substance of sodium formiate and volatile salt then with sal volatile, obtain containing the solution of ammonium formiate and yellow soda ash, after filtration, obtain extremely a spot of filter cake impurity and clarifying filtrate three;

Step D: filtrate three is saturated solution of sodium carbonate through underpressure distillation, is cooled to 0 ℃, and at this moment, the saturation ratio of yellow soda ash is 7.0g, the saturation ratio of ammonium formiate is 102g, and therefore, crystallize sodium carbonate is separated out, and ammonium formiate separates still in solution after filtration, obtains crystals of sodium carbonate and filtrate four; Filtrate four further underpressure distillation are the ammonium formiate supersaturated solution, are cooled to 0 ℃, and at this moment, because the content of yellow soda ash is few in this moment solution, therefore, the ammonium formiate mass crystallization is separated out, and separates after filtration, obtains the ammonium formiate crystal; Crystals of sodium carbonate and ammonium formiate crystal advance washing, dry and pulverizing respectively, thereby obtain yellow soda ash product and ammonium formiate product respectively; The quality of the pure substance of the yellow soda ash that it contains is 106kg, and the quality of the pure substance of the ammonium formiate that it contains is 126kg.

Embodiment 3: a kind of method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash, wherein, sodium formiate 25wt.%, tetramethylolmethane 7wt.%, its raw material are that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid, comprise the steps:

Steps A: formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid 544kg, are the tetramethylolmethane saturated solution through underpressure distillation, and postcooling, the tetramethylolmethane crystallization is separated out, and separates after filtration, obtains crystals of pentaerythritol and filtrate one; Filtrate one further underpressure distillation is the sodium formiate saturated solution, and postcooling, the sodium formiate crystallization is separated out, and is separating after filtration, obtains sodium formiate crystal and filtrate two;

Step B: the above-mentioned crystals of pentaerythritol that obtains through washing, dry and pulverizing, is obtained the tetramethylolmethane product; The quality of the tetramethylolmethane pure substance that it contains is 38.08kg;

Step C: the above-mentioned sodium formiate crystal that obtains is water-soluble, be reaction in 2: 0.8 with the ratio of the molar content of the pure substance of sodium formiate and volatile salt then with sal volatile, obtain containing the solution of ammonium formiate and yellow soda ash, after filtration, obtain extremely a spot of filter cake impurity and clarifying filtrate three;

Step D: filtrate three is saturated solution of sodium carbonate through underpressure distillation, is cooled to 0 ℃, and at this moment, the saturation ratio of yellow soda ash is 7.0g, the saturation ratio of ammonium formiate is 102g, and therefore, crystallize sodium carbonate is separated out, and ammonium formiate separates still in solution after filtration, obtains crystals of sodium carbonate and filtrate four; Filtrate four further underpressure distillation are the ammonium formiate supersaturated solution, are cooled to 0 ℃, and at this moment, because the content of yellow soda ash is few in this moment solution, therefore, the ammonium formiate mass crystallization is separated out, and separates after filtration, obtains the ammonium formiate crystal; Crystals of sodium carbonate and ammonium formiate crystal advance washing, dry and pulverizing respectively, thereby obtain yellow soda ash product and ammonium formiate product respectively; The quality of the pure substance of the yellow soda ash that it contains is 84.8kg, and the quality of the pure substance of the ammonium formiate that it contains is 100.8kg.

Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.

Claims (1)

1. a method for preparing tetramethylolmethane coproduction ammonium formiate and yellow soda ash is characterized in that, its raw material is that formaldehyde and acetaldehyde condensation are produced tetramethylolmethane gained waste liquid, comprises the steps:

Steps A: is the tetramethylolmethane saturated solution with formaldehyde and acetaldehyde condensation production tetramethylolmethane gained waste liquid through underpressure distillation, and postcooling, the tetramethylolmethane crystallization is separated out, and separates after filtration, obtains crystals of pentaerythritol and filtrate one; Filtrate one further underpressure distillation is the sodium formiate saturated solution, and postcooling, the sodium formiate crystallization is separated out, and is separating after filtration, obtains sodium formiate crystal and filtrate two;

Step B: the above-mentioned crystals of pentaerythritol that obtains through washing, dry and pulverizing, is obtained the tetramethylolmethane product;

Step C: the above-mentioned sodium formiate crystal that obtains is water-soluble, it is 2 with the ratio of the molar content of the pure substance of sodium formiate and volatile salt then: the 0.8-1.2 reaction with sal volatile, obtain containing the solution of ammonium formiate and yellow soda ash, after filtration, obtain extremely a spot of filter cake impurity and clarifying filtrate three;

Step D: filtrate three is saturated solution of sodium carbonate through underpressure distillation, is cooled to 0 ℃, and at this moment, the saturation ratio of yellow soda ash is 7.0g, the saturation ratio of ammonium formiate is 102g, and therefore, crystallize sodium carbonate is separated out, and ammonium formiate separates still in solution after filtration, obtains crystals of sodium carbonate and filtrate four; Filtrate four further underpressure distillation are the ammonium formiate supersaturated solution, are cooled to 0 ℃, and at this moment, because the content of yellow soda ash is few in this moment solution, therefore, the ammonium formiate mass crystallization is separated out, and separates after filtration, obtains the ammonium formiate crystal; Crystals of sodium carbonate and ammonium formiate crystal advance washing, dry and pulverizing respectively, thereby obtain yellow soda ash product and ammonium formiate product respectively.