CN101671233B - Method for producing sodium formate - Google Patents
Method for producing sodium formate Download PDFInfo
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- CN101671233B CN101671233B CN 200910182420 CN200910182420A CN101671233B CN 101671233 B CN101671233 B CN 101671233B CN 200910182420 CN200910182420 CN 200910182420 CN 200910182420 A CN200910182420 A CN 200910182420A CN 101671233 B CN101671233 B CN 101671233B
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Abstract
The invention relates to a method for producing sodium formate, and comprises the following technique processes: 1. taking n-butanal, formaldehyde solution and caustic soda liquid as raw materials, carrying out low temperature condensation to obtain a condensation solution, and acidating with formic acid followed by pre-treatment; 2. concentrating the condensation solution; 3. extracting the condensation solution in an extracting tower with an alcohol organic solvent containing 5-9 carbon atoms, leading the organic phase after extracting into the bottom part of a bath tower, amplifying the inner diameter dimension of the top part of the bath tower accounting for 5-30% of the height range of the bath tower by 10-50%, carrying out countercurrent washing on the organic phase by using de-ionized water or aqueous solution saturated by trimethylolpropane, the aqueous phase after washing into the upper part of the extracting tower to countercurrent contact with an extract and an oil phase entering afterwards; 5. transferring the extracted aqueous phase into an evaporating kettle to concentrate the sodium formate solution; 5. after relieving vacuum, transferring the concentrated sodium formate solution into a crystallizing kettle, and cooling to below 37 DEG C; 6. centrifuging; and 7. drying. The method of the invention can guarantee the quality of the main product trimethylolpropane and enhance the yield and quality of sodium formate.
Description
(1) technical field
The present invention relates to a kind of method of producing sodium formiate, especially the method for by-product sodium formiate when producing polyvalent alcohol.Belong to organic chemical industry's product technical field.
(2) background technology
Sodium formiate is one of main raw material of producing formic acid and oxalic acid, also is the raw material of producing vat powder.In leather processing, dope dyeing and electroplating industry, it is used separately as rawhide treatment agent, dye leveller and promotor.It can also be used for the delustring of Zantrel.Because it can resolve into hydrogen and sodium hydrogencarbonate at low temperatures, so it still is a kind of material of storing hydrogen.
Producing sodium formiate in the industry can liquid caustic soda be raw material with coke, through gas making, dedusting, causticization, join alkali, coal gas compression, synthesize, processes such as evaporation concentration, separation, oven dry produce sodium formiate.But along with the development of polyvalent alcohol product, sodium formiate more is a by-product in the production process of polyvalent alcohol.Chinese patent 200910032759.7 has been described a kind of low temperature condensation and condensated liquid has been carried out pretreated method.In the method, if the alkali hydroxide soln of selecting for use is a liquid caustic soda, then when obtaining TriMethylolPropane(TMP), by-product be exactly sodium formiate.
Chinese patent 200510133648.7 described a kind of from reaction mixture the method for isolation of trimethylolpropane and sodium formiate; The technical scheme of being taked is: adopt knockdown extraction tank; From the condensated liquid that is in water, extract TriMethylolPropane(TMP) with water-fast organic solvent, what aqueous phase was remaining is exactly the solution that contains sodium formiate.But the problem of a maximum of this method is exactly owing to the organic phase after the extraction is not washed, not only still can be mixed with the part sodium formiate in the organic phase, and the sodium formiate of aqueous phase also to have loss, the yield decline of sodium formiate.And fact proved of polyvalent alcohol production industry even only contain a spot of sodium formiate in the organic phase, also can promote the decomposition of polyvalent alcohol when being heated in the sepn process of road, back polyvalent alcohol, influences the quality product of polyvalent alcohol.
(3) summary of the invention
The objective of the invention is to overcome above-mentioned deficiency, a kind of quality that had both guaranteed the major product polyvalent alcohol is provided, can improve the method for the by-product sodium formiate of sodium formiate yield and quality again.
The objective of the invention is to realize like this: a kind of method of producing sodium formiate, said method mainly comprise following technological processs:
Step 1, the formaldehyde solution of massfraction>=20% is diluted to massfraction is 3～15% concentration, then that it is freezing to 4～20 ℃, changes the condensation still over to; With the butyraldehyde-n and the liquid caustic soda separated into two parts of calculated mass, the first part of butyraldehyde-n is 1/2～1 of a butyraldehyde-n calculated mass, and remaining is second section; The first part of liquid caustic soda is 1/5～1/2 of a liquid caustic soda calculated mass, and remaining is second section, and the joining day also is divided into two parts; The first part that in first 1～70min, at the uniform velocity adds butyraldehyde-n and liquid caustic soda; The second section that in second 1～70min, at the uniform velocity adds butyraldehyde-n and liquid caustic soda, the continued that finishes of feeding intake is kept whipped state 0.25～1h, condensated liquid; In condensated liquid, drip formic acid then; Reach 5.0～7.0 up to the pH of condensated liquid value, remove the pre-treatment of formaldehyde, methyl alcohol and portion water then, obtain the condensated liquid of massfraction≤0.02% of residual formaldehyde;
Step 2, employing multiple-effect evaporator; Head imitate vacuum tightness be-0.005～-0.04MPa, first imitate liquidus temperature be 100～130 ℃, first imitate gas phase temperature be 90～115 ℃, end imitate vacuum tightness be-0.08～-to imitate liquidus temperature be that to imitate gas phase temperature be concentrated pretreated condensated liquid under 40～55 ℃ the condition for 45～60 ℃, end for 0.098MPa, end; Make that the massfraction of TriMethylolPropane(TMP) reaches 45～50% in the condensated liquid, the concentration of sodium formiate also is improved;
The alcohol organic solvent that step 3, usefulness contain 5～9 carbon atoms extracts liquid concentrator in extraction tower; The organic phase that extraction obtains gets into the water wash column bottom; The water wash column internal diameter size that the water wash column top accounts in water wash column height 5～30% scopes amplifies 10～50%; With deionized water or by the saturated aqueous solution countercurrent washing organic phase of TriMethylolPropane(TMP), deionized water or got into by " neck " of the saturated aqueous solution of TriMethylolPropane(TMP) from the adjacent internal diameter amplifier section of water wash column bottom is because density flows downward greater than oil phase; Make the sodium formiate in the organic phase change water fully over to contact exchange with organic phase after; Water after the washing gets into the top of extraction tower, with extraction agent that continues to come in and oil phase counter current contact, makes the organic compositions such as TriMethylolPropane(TMP) of aqueous phase change in the oil phase fully; When the water that is extracted flows out from the extraction tower bottom, become mainly to contain the aqueous solution of sodium formiate;
Step 4, the water that is extracted is changed in the evaporating kettle,, evaporate under 80～110 ℃ the temperature, sodium formate solution is concentrated, in solution, begin to have the small quantities of particles thing to occur at the pressure of 0.04～0.06MPa;
Step 5, evaporating kettle let out vacuum after, spissated sodium formate solution is changed in the crystallization kettle, with recirculated cooling water it is cooled to below 37 ℃, make the sodium formiate crystallization abundant;
Step 6, change the material after the crystallization over to whizzer; Carry out spinning; The solid phase that obtains promptly is the sodium formiate that contains partial crystallization water, and after centrifugal mother liquor of telling and the merging of the water from extraction tower, proceeds sodium formiate evaporation, crystallization and the centrifugal process of next round;
Step 7, the sodium formiate that will contain crystal water changes dryer over to dries, and the massfraction that can obtain moisture and volatile matter content is lower than 1%, the product of the massfraction of butt sodium formiate >=98.0%.
The alcohol organic solvent of 5～9 carbon atoms that use in the above-mentioned steps three can be following a kind of: amylalcohol, cyclopentanol, hexanol, hexalin, enanthol, n-Octanol and 2-Ethylhexyl Alcohol.
Compared with prior art, the present invention has advantage:
1) adopts the low temperature condensation to reduce side reaction as much as possible, make the organic impurities that contains in the sodium formiate of producing few.
2) condensated liquid is carried out concentration, can avoid using high amounts of solvents in the subsequent separation process and producing a large amount of sewage, and can be used for back joining rare formaldehyde solution after the condensate moisture that steams, realized the recycle and the cleaner production of material.
3) internal diameter with the water wash column top suitably amplifies; Help making the oil phase flow velocity that arrives the top to slow down; Make the small amount of aqueous phase of being carried secretly up in this part tower body, continue layering, flow downward by oil phase; The sodium formiate that aqueous phase is carried secretly also no longer gets into the Purification of Trimethylolpropane operation with oil phase, and it is many that the sodium formiate that aqueous phase reclaims becomes.
4) crystallization, the sodium formiate after centrifugal can reach the commercial requirement of massfraction >=94% of butt sodium formiate, pass through after one baking operation again, can further improve the massfraction of butt sodium formiate, satisfy the demand of high-end customer.
(4) embodiment
Step 1, be that 37% formaldehyde solution pumps into the batching still with the 1300kg massfraction, add the water distribution of returning that obtains after the condensate moisture that steams in the following concentration process of 2000kg, rest part is supplied with deionized water; Join to such an extent that the 6000kg massfraction is rare formaldehyde solution of 8%, it is freezing to 12 ℃, change the condensation still over to; The butyraldehyde-n of 360kg massfraction >=99% is divided into 270kg and 90kg two portions, is that 32% liquid caustic soda also is divided into 250kg and 500kg two portions with the 750kg massfraction, in preceding 1h; Speed with 270kg/h in the condensation still is thrown butyraldehyde-n, throws liquid caustic soda with the speed of 250kg/h, in 0.5h subsequently; Speed with 180kg/h is thrown butyraldehyde-n, throws liquid caustic soda with the speed of 1000kg/h, and the continued stirring 0.5h that finishes feeds intake; Obtain condensated liquid, in condensated liquid, drip formic acid then, reach 5.4 up to the pH of condensated liquid value; Then condensated liquid is removed the pre-treatment of formaldehyde, methyl alcohol and portion water, obtain residual formaldehyde and contain the condensated liquid that measurement is not come out;
Step 2, employing quadruple effect evaporator; Head imitate vacuum tightness be-0.01～-0.02MPa, first imitate liquidus temperature be 115～125 ℃, first imitate gas phase temperature be 97～105 ℃, end imitate vacuum tightness be-0.09～-to imitate liquidus temperature be that 47～52 ℃, end effect gas phase temperature are under 45～50 ℃ the condition condensated liquid to be concentrated for 0.095MPa, end; Make TriMethylolPropane(TMP) massfraction wherein reach 48%, the concentration of sodium formiate also is improved;
Step 3, with 2-Ethylhexyl Alcohol as extraction agent, the organic composition of extraction in the liquid concentrator in extraction tower, the organic phase that extraction obtains gets into the water wash column bottom; The internal diameter of the conventional part of water wash column is 1.4M; The internal diameter that the water wash column top accounts in water wash column height 10% scope is amplified to 1.8M, has promptly amplified 28.6%, with deionized water countercurrent washing organic phase; Deionized water gets into from " neck " of the adjacent internal diameter amplifier section of water wash column bottom; Because density flows downward greater than oil phase, make the sodium formiate in the organic phase change water fully over to contact exchange with organic phase after, the water after the washing gets into the top of extraction tower; With extraction agent that continues to come in and oil phase counter current contact; The organic compositions such as TriMethylolPropane(TMP) of aqueous phase are changed in the oil phase fully, when the water that is extracted flows out from the extraction tower bottom, become mainly to contain the aqueous solution of sodium formiate;
Step 4, the water that is extracted is changed in the evaporating kettle,, evaporate under 98 ℃ the temperature, sodium formate solution is concentrated, in solution, begin to have the small quantities of particles thing to occur at the pressure of 0.05MPa;
Step 5, evaporating kettle let out vacuum after, spissated sodium formate solution is changed in the crystallization kettle, with recirculated cooling water it is cooled to 35 ℃, make the sodium formiate crystallization abundant;
Step 6, change the material after the crystallization over to whizzer; Carry out spinning; The solid phase that obtains promptly is the sodium formiate that contains partial crystallization water, and after centrifugal mother liquor of telling and the merging of the water from extraction tower, proceeds sodium formiate evaporation, crystallization and the centrifugal process of next round;
Step 7, the sodium formiate that will contain crystal water changes dryer over to dries, and the massfraction that can obtain moisture and volatile matter content is 0.29%, and the massfraction of butt sodium formiate is 98.57% product.
The 2-Ethylhexyl Alcohol that uses in the above-mentioned steps three also can change does a kind of in amylalcohol, cyclopentanol, hexanol, hexalin, enanthol or the n-Octanol.
Claims (1)
1. method of producing sodium formiate is characterized in that said method mainly comprises following technological processs:
Step 1, the formaldehyde solution of massfraction>=20% is diluted to massfraction is 3～15% concentration, then that it is freezing to 4～20 ℃, changes the condensation still over to; With the butyraldehyde-n and the liquid caustic soda separated into two parts of calculated mass, the first part of butyraldehyde-n is 1/2～1 of a butyraldehyde-n calculated mass, and remaining is second section; The first part of liquid caustic soda is 1/5～1/2 of a liquid caustic soda calculated mass, and remaining is second section, and the joining day also is divided into two parts; The first part that in first 1～70min, at the uniform velocity adds butyraldehyde-n and liquid caustic soda; The second section that in second 1～70min, at the uniform velocity adds butyraldehyde-n and liquid caustic soda, the continued that finishes of feeding intake is kept whipped state 0.25～1h, condensated liquid; In condensated liquid, drip formic acid then; Reach 5.0～7.0 up to the pH of condensated liquid value, remove the pre-treatment of formaldehyde, methyl alcohol and portion water then, obtain the condensated liquid of massfraction≤0.02% of residual formaldehyde;
Step 2, employing multiple-effect evaporator; Head imitate vacuum tightness be-0.005～-0.04MPa, first imitate liquidus temperature be 100～130 ℃, first imitate gas phase temperature be 90～115 ℃, end imitate vacuum tightness be-0.08～-to imitate liquidus temperature be that to imitate gas phase temperature be concentrated pretreated condensated liquid under 40～55 ℃ the condition for 45～60 ℃, end for 0.098MPa, end; Make that the massfraction of TriMethylolPropane(TMP) reaches 45～50% in the condensated liquid, the concentration of sodium formiate also is improved;
The alcohol organic solvent that step 3, usefulness contain 5～9 carbon atoms extracts liquid concentrator in extraction tower; The organic phase that extraction obtains gets into the water wash column bottom; The water wash column internal diameter size that the water wash column top accounts in water wash column height 5～30% scopes amplifies 10～50%; With deionized water or by the saturated aqueous solution countercurrent washing organic phase of TriMethylolPropane(TMP), deionized water or got into by " neck " of the saturated aqueous solution of TriMethylolPropane(TMP) from the adjacent internal diameter amplifier section of water wash column bottom is because density flows downward greater than oil phase; Make the sodium formiate in the organic phase change water fully over to contact exchange with organic phase after; Water after the washing gets into the top of extraction tower, with extraction agent that continues to come in and oil phase counter current contact, makes the organic compositions such as TriMethylolPropane(TMP) of aqueous phase change in the oil phase fully; When the water that is extracted flows out from the extraction tower bottom, become mainly to contain the aqueous solution of sodium formiate;
Step 4, the water that is extracted is changed in the evaporating kettle,, evaporate under 80～110 ℃ the temperature, sodium formate solution is concentrated, in solution, begin to have the small quantities of particles thing to occur at the pressure of 0.04～0.06MPa;
Step 5, evaporating kettle let out vacuum after, spissated sodium formate solution is changed in the crystallization kettle, with recirculated cooling water it is cooled to below 37 ℃, make the sodium formiate crystallization abundant;
Step 6, change the material after the crystallization over to whizzer; Carry out spinning; The solid phase that obtains promptly is the sodium formiate that contains partial crystallization water, and after centrifugal mother liquor of telling and the merging of the water from extraction tower, proceeds sodium formiate evaporation, crystallization and the centrifugal process of next round;
Step 7, the sodium formiate that will contain crystal water changes dryer over to dries;
The alcohol organic solvent of 5～9 carbon atoms that use in the above-mentioned steps three is following a kind of: amylalcohol, cyclopentanol, hexanol, hexalin, enanthol, n-Octanol and 2-Ethylhexyl Alcohol.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102795964B (en) * | 2012-09-12 | 2013-05-29 | 江西高信有机化工有限公司 | 20000-ton-annual-yield production technique of trimethylolpropane by calcium method |
| CN104027992A (en) * | 2014-03-07 | 2014-09-10 | 中盐安徽红四方股份有限公司 | A novel method of continuous evaporation to prepare sodium formate |
| CN106800507A (en) * | 2015-11-25 | 2017-06-06 | 衡阳屹顺化工有限公司 | A kind of solid-liquid separating method produced during sodium formate |
| CN106748738A (en) * | 2015-11-25 | 2017-05-31 | 衡阳屹顺化工有限公司 | A kind of Optimized Extraction technique of separating formic sodium |
| CN106146293A (en) * | 2016-05-20 | 2016-11-23 | 百川化工(如皋)有限公司 | Process for reducing color number of sodium formate |
| CN110156565A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | Trimethylolpropane extraction and water washing method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776963A (en) * | 1971-03-16 | 1973-12-04 | Celanese Corp | Trimethylolpropane recovery |
| CN1076185A (en) * | 1993-01-08 | 1993-09-15 | 北京市助剂研究所 | The TriMethylolPropane(TMP) production technique is improved |
| US6316679B1 (en) * | 1999-06-01 | 2001-11-13 | Celanese International Corporation | Treatment of a composition comprising a trimethylolalkane bis-monolinear formal |
| CN1803745A (en) * | 2005-12-27 | 2006-07-19 | 天津天大天海化工新技术有限公司 | Method for the isolation of trimethylolpropane and sodium formate from a reaction mixture |
| CN101092328A (en) * | 2006-06-22 | 2007-12-26 | 湖北宜化集团有限责任公司 | Method for preparing trimethylolpropane in high purity, and low chroma |
-
2009
- 2009-09-14 CN CN 200910182420 patent/CN101671233B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3776963A (en) * | 1971-03-16 | 1973-12-04 | Celanese Corp | Trimethylolpropane recovery |
| CN1076185A (en) * | 1993-01-08 | 1993-09-15 | 北京市助剂研究所 | The TriMethylolPropane(TMP) production technique is improved |
| US6316679B1 (en) * | 1999-06-01 | 2001-11-13 | Celanese International Corporation | Treatment of a composition comprising a trimethylolalkane bis-monolinear formal |
| CN1803745A (en) * | 2005-12-27 | 2006-07-19 | 天津天大天海化工新技术有限公司 | Method for the isolation of trimethylolpropane and sodium formate from a reaction mixture |
| CN101092328A (en) * | 2006-06-22 | 2007-12-26 | 湖北宜化集团有限责任公司 | Method for preparing trimethylolpropane in high purity, and low chroma |
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