CN100368371C - Method for preparing calcium formate - Google Patents
Method for preparing calcium formate Download PDFInfo
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- CN100368371C CN100368371C CNB2005100180645A CN200510018064A CN100368371C CN 100368371 C CN100368371 C CN 100368371C CN B2005100180645 A CNB2005100180645 A CN B2005100180645A CN 200510018064 A CN200510018064 A CN 200510018064A CN 100368371 C CN100368371 C CN 100368371C
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- calcium formiate
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- acetaldehyde
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- formaldehyde
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Abstract
The present invention relates to a calcium formate producing method which belongs to the technical field of chemical product producing methods. Calcium formate is an organic chemical raw material having wide application. Calcium formate products produced by the present method have high cost and multiple impurities. The technology of the present invention uses formaldehyde, acetaldehyde and calcium hydroxide for condensation reaction according to the substance amount proportion of 4.2-8: 1: 0.5-0.6 in order to further react with formic acid. The present invention has the technological processes that the acetaldehyde, the formaldehyde, the calcium hydroxide and the formic acid are added to a condensation kettle for reaction according to the proportion, temperature is controlled from 16 DEG C to 80 DEG C, and reaction time is from 1.5 h to 4 h. Solution is neutral after reaction is completed, and obtained solution is concentrated by vacuum and centrifugally dried to generate calcium formate after pressurized and distilled. Main centrifugal solution can generate pentaerythrite after reclamation. The novel technology having the advantages of low production cost, few impurities, high yield, less investment, obvious effect, etc., raw materials can be easily obtained, and the present invention has favorable industrial development prospect.
Description
One. technical field: the present invention relates to prepare the method for calcium formiate, relate in particular to acetaldehyde, formaldehyde, formic acid be raw material under the effect of calcium hydroxide, prepare the method for calcium formiate.
Two. background technology: calcium formiate is a kind of purposes Organic Chemicals comparatively widely, can do the feed anticorrosion agent, cement early strength agent, processing aid in the leather industry, the auxiliary agent that burmished paper is produced, lubricant, petroleum industry probing auxiliary agent, crop growth mediator agent; The byproduct tetramethylolmethane can be used to make high ucon oil, Synolac, fire retardant material and medicine and explosive etc.At present, the preparation of relevant calcium formiate both at home and abroad mainly contains three types method, and one type is to adopt acid-base neutralisation prepared in reaction calcium formiate, comprises that formic acid and calcium carbonate reaction, formic acid and calcium oxide reaction, formic acid and calcium hydroxide reaction prepare calcium formiate.Disclose the method that is prepared calcium formiate by formic acid and lime carbonate, calcium hydroxide reaction in prior art CN 1184184C, this invention mainly is to change production technique, has realized serialization, the large-scale production of calcium formiate preparation.But because formic acid itself is to make methyl-formiate by the sodium formiate acidifying or by the CO synthesis gas, hydrolysis and getting again, cost is higher, and product content is low, impurity is many.Another kind of type is to adopt Ca (OH)
2Under the effect of catalyzer, prepare with formaldehyde reaction.Adopt this method, every production 1mol calcium formiate, produce 2mol methyl alcohol, this makes the formaldehyde consumption increase, also to separate residual formaldehyde in the by-product carbinol of generation and the reaction solution on the other hand, otherwise calcium formiate is difficult for crystallization separates out, and formaldehyde easy polymerization reaction take place under the katalysis of alkali, and operation brings very big difficulty to actual industrial.The third type is to prepare calcium formiate under the effect of superoxide.This method is to adopt in the aqueous solution with Ca (OH)
2, formaldehyde, H
2O
2The prepared in reaction calcium formiate adopts this method so also significantly to have increased cost with a large amount of superoxide, and still has formaldehyde saccharification and the incomplete problem of reaction.
Three. summary of the invention:
The objective of the invention is: overcome cost height in the existing calcium formiate preparation, defective such as yield is low provides a kind of preparation technology simple, the method for preparing calcium formiate that raw material is common.
Technical scheme of the present invention is:
A kind of method for preparing calcium formiate, this method is with formaldehyde, acetaldehyde and calcium hydroxide are that raw material carries out condensation reaction, the steps include: earlier concentration to be that the formaldehyde solution of 120～150g/L adds and has in the reactor of agitator, slowly add the acetaldehyde solution of 180～220g/L and the aqua calcis of 180～220g/L and carry out condensation reaction, formaldehyde, acetaldehyde, the ratio of the amount of substance of calcium hydroxide is 4.2～8: 1: 0.5～0.6 and 85% formic acid further reacts, temperature is controlled at 16～80 ℃, reaction finishing control solution be neutrality, with gained solution through pressure distillation, vacuum concentration, centrifugal drying, the output calcium formiate.
Described acetaldehyde solution, formaldehyde solution, aqua calcis, formic acid adopt the mode that drips to add.
Dropping acetaldehyde and calcium hydroxide are continous way or change a kind of rate of addition at least in formaldehyde solution.
The described method for preparing calcium formiate, the kilogram volume ratio is 1: 1.1～2.0.
The described method for preparing calcium formiate is reflected in the open reactor and carries out.
The described method for preparing calcium formiate, with the formic acid reaction, the reaction times is 1.5～4 hours, the pH value of control solution is 6.5～7.5.
The described method for preparing calcium formiate, condensated liquid are advanced distillation tower and are carried out pressure distillation.
The calcium formiate mother liquor is reclaimed output tetramethylolmethane byproduct.
Positive beneficial effect of the present invention is:
1. adopt the preparation method of calcium formiate of the present invention, production cost is low, not only can obtain content and be 96%～99.5% calcium formiate, can also be by recovery to the calcium formiate mother liquor, obtain single cropping content and be 94%～98.5% byproduct tetramethylolmethane.
2. adopt the preparation method of calcium formiate of the present invention, the products obtained therefrom foreign matter content is few, and product yield height, the yield of calcium formiate are more than 96%, and the yield of byproduct tetramethylolmethane is also more than 96%.
3. this raw materials technology is easy to get, and low price can be realized serialization, large-scale production, can save a large amount of energy consumptions, meets national energy saving policy, has less investment, and characteristics such as instant effect have the favorable industrial development prospect.
Four. embodiment:
Example one: the formaldehyde solution 2.94L that in the uncovered reactor that has agitator to stir, adds 150g/L, be cooled to 30 ℃, the aqua calcis 0.63L that adds 220g/L simultaneously, the acetaldehyde solution 0.7L of 220g/L, total charging capacity 3.5mol, kilogram volume ratio 1: 1.4, the amount of substance ratio that feeds intake is 4.2: 1: 0.54.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 50 ℃ of end reaction temperature, and insulation 0.5h is warming up to 60 ℃, adds 85% formic acid 0.35L and is neutralized to PH=6.5.With vacuum-evaporation to proportion 1.10, centrifugal the calcium formiate of heat, quality index is as follows:
Calcium formiate: 97.5%, organism: 2.0%, moisture content: 0.5%, yield: 96% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 94.3%, hydroxyl: 47.7%, two seasons: 2.5%, other: 3.0%, yield: 94%.
Example two: the formaldehyde solution 3.68L that in the uncovered reactor that has agitator to stir, adds 160g/L, be cooled to 20 ℃, the aqua calcis 0.6L that adds 240g/L simultaneously, the acetaldehyde solution 0.64L of 240g/L, total charging capacity 3.5mol, kilogram volume ratio 1: 1.4, the amount of substance ratio that feeds intake is 5.6: 1: 0.56.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 48 ℃ of end reaction temperature, and insulation 0.5h is warming up to 60 ℃, adds 85% formic acid 0.35L and is neutralized to PH=7.5.Distillation back with vacuum-evaporation to proportion 1.10, heat centrifugal calcium formiate, quality index is as follows:
Calcium formiate: 98.0%, organism: 1.8%, moisture content: 0.3%, yield: 96.5% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 95.5%, hydroxyl: 48.0%, two seasons: 2.5%, other: 2.0%, yield: 96.5%.
Example three: the formaldehyde solution 3.92L that in the uncovered reactor that has agitator to stir, adds 150g/L, be cooled to 20 ℃, the aqua calcis 0.68L that adds 210g/L simultaneously, the acetaldehyde solution 0.734L of 210g/L, total charging capacity 3.5mol, kilogram volume ratio 1: 1.5, the amount of substance ratio that feeds intake is 5.6: 1: 0.56.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 48 ℃ of end reaction temperature, and insulation 0.5h is warming up to 80 ℃, adds 85% formic acid 0.35L and is neutralized to PH=6.8.Distillation back with vacuum-evaporation to proportion 1.10, heat centrifugal calcium formiate, quality index is as follows:
Calcium formiate: 98.2%, organism: 1.5%, moisture content: 0.3%, yield: 97% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 96%, hydroxyl: 48.2%, two seasons: 2.0%, other: 2.0%, yield: 96.5%.
Example four: the formaldehyde solution 3.97L that in the uncovered reactor that has agitator to stir, adds 180g/L, be cooled to 16 ℃, the aqua calcis 0.65L that adds 240g/L simultaneously, the acetaldehyde solution 0.64L of 240g/L, total charging capacity 3.5mol, kilogram volume ratio 1: 1.5, the amount of substance ratio that feeds intake is 6.8: 1: 0.6.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 32 ℃ of end reaction temperature, and insulation 0.5h is warming up to 60 ℃, adds 85% formic acid 0.4L and is neutralized to PH=6.5.Distillation back with vacuum-evaporation to proportion 1.10, heat centrifugal calcium formiate, quality index is as follows:
Calcium formiate: 98.5%, organism: 1.1%, moisture content: 0.2%, yield: 97.4% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 96.8%, hydroxyl: 48.2%, two seasons: 1.4%, other: 0.8%, yield: 97%
Example five: the formaldehyde solution 5.1L that in the uncovered reactor that has agitator to stir, adds 140g/L, be cooled to 16 ℃, the aqua calcis 0.78L that adds 200g/L simultaneously, the acetaldehyde solution 0.77L of 200g/L, total charging capacity 3.5mol, the kilogram volume ratio amount of substance ratio that feeds intake at 1: 1.9 is 6.8: 1: 0.6.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 32 ℃ of end reaction temperature, and insulation 0.5h is warming up to 60 ℃, adds 85% formic acid 0.4L and is neutralized to PH=6.5.Distillation back with vacuum-evaporation to proportion 1.10, heat centrifugal calcium formiate, quality index is as follows:
Calcium formiate: 99%, organism: 0.7%, moisture content: 0.2%, yield: 98% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 98%, hydroxyl: 48.5%, two seasons: 1.2%, other: 0.8%, yield: 97%
Example six: the formaldehyde solution 5.6L that in the uncovered reactor that has agitator to stir, adds 150g/L, be cooled to 16 ℃, the aqua calcis 0.78L that adds 200g/L simultaneously, the acetaldehyde solution 0.77L of 200g/L, total charging capacity 3.5mol, kilogram volume ratio 1: 2.0, the amount of substance ratio that feeds intake is 8.0: 1: 0.6.By means of reaction heat, reaction mass begins to heat up, and 0.5h has all thrown, 32 ℃ of end reaction temperature, and insulation 0.5h is warming up to 60 ℃, adds 85% formic acid 0.4L and is neutralized to PH=7.2.Distillation back with vacuum-evaporation to proportion 1.10, heat centrifugal calcium formiate, quality index is as follows:
Calcium formiate: 99.3%, organism: 0.5%, moisture content: 0.2%, yield: 98% calcium formiate mother liquor crystallization, 30 ℃ of centrifugal substandard goods tetramethylolmethanes that get, quality index is as follows:
Single cropping: 98.5%, hydroxyl: 48.8%, two seasons: 0.7%, other: 0.8%, yield: 97.5%
Claims (7)
1. method for preparing calcium formiate, this method is with formaldehyde, acetaldehyde and calcium hydroxide are that raw material carries out condensation reaction, it is characterized in that: be concentration that the formaldehyde solution of 120～150g/L adds and has in the reactor of agitator earlier, slowly add the acetaldehyde solution of 180～220g/L and the aqua calcis of 180～220g/L and carry out condensation reaction, formaldehyde, acetaldehyde, the ratio of the amount of substance of calcium hydroxide is 4.2～8: 1: 0.5～0.6 and 85% formic acid further reacts, temperature is controlled at 16～80 ℃, reaction finishing control solution be neutrality, with gained solution through pressure distillation, vacuum concentration, centrifugal drying, the output calcium formiate.
2. the method for preparing calcium formiate according to claim 1 is characterized in that: acetaldehyde solution, and formaldehyde solution, aqua calcis, formic acid adopt the mode that drips to add.
3. the method for preparing calcium formiate according to claim 1 is characterized in that: dropping acetaldehyde and calcium hydroxide are continous way or change a kind of rate of addition at least in formaldehyde solution.
4. the method for preparing calcium formiate according to claim 1 is characterized in that: be reflected in the open reactor and carry out.
5. the method for preparing calcium formiate according to claim 1 is characterized in that: with the formic acid reaction, the reaction times is 1.5～4 hours, and the pH value of control solution is 6.5～7.5.
6. the method for preparing calcium formiate according to claim 1 is characterized in that: condensated liquid advances distillation tower and carries out pressure distillation.
7. the method for preparing calcium formiate according to claim 1 is characterized in that: the calcium formiate mother liquor is reclaimed output tetramethylolmethane byproduct.
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| CNB2005100180645A CN100368371C (en) | 2005-09-29 | 2005-09-29 | Method for preparing calcium formate |
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|---|---|---|---|
| CNB2005100180645A CN100368371C (en) | 2005-09-29 | 2005-09-29 | Method for preparing calcium formate |
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| CN1762963A CN1762963A (en) | 2006-04-26 |
| CN100368371C true CN100368371C (en) | 2008-02-13 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104496757B (en) * | 2014-12-24 | 2016-02-24 | 保定市国秀化工有限责任公司 | Improve the method for the calcareous amount of calcium method tetramethylolmethane byproduct formic acid |
| CN104726937B (en) * | 2015-03-09 | 2017-05-03 | 孙王淇 | Calcium formate single crystal optical material and preparation method thereof |
| CN113248363B (en) * | 2021-05-17 | 2022-11-01 | 昌德新材科技股份有限公司 | Recycling method of methyl formate waste liquid |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1050648A (en) * | 1963-05-31 | |||
| GB732015A (en) * | 1952-07-03 | 1955-06-15 | Degussa | Process for the production of pentaerythritol |
| GB848632A (en) * | 1958-04-30 | 1960-09-21 | Montedison Spa | Method of recovering pentaerythritol and alkaline formates |
| EP0510375A1 (en) * | 1991-04-25 | 1992-10-28 | Degussa Ag | Process for preparing calcium formate |
| CN1165804A (en) * | 1996-05-22 | 1997-11-26 | Y·诺夫达德斯专利公司 | Process for preparation of pentaerythritol |
| CN1472186A (en) * | 2003-06-30 | 2004-02-04 | 孙宝远 | Method for producing calcium formate |
| CN1651373A (en) * | 2004-12-03 | 2005-08-10 | 王永军 | Production technology of tetramethylol methane by using ealcium method |
-
2005
- 2005-09-29 CN CNB2005100180645A patent/CN100368371C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB732015A (en) * | 1952-07-03 | 1955-06-15 | Degussa | Process for the production of pentaerythritol |
| GB848632A (en) * | 1958-04-30 | 1960-09-21 | Montedison Spa | Method of recovering pentaerythritol and alkaline formates |
| GB1050648A (en) * | 1963-05-31 | |||
| EP0510375A1 (en) * | 1991-04-25 | 1992-10-28 | Degussa Ag | Process for preparing calcium formate |
| CN1165804A (en) * | 1996-05-22 | 1997-11-26 | Y·诺夫达德斯专利公司 | Process for preparation of pentaerythritol |
| CN1472186A (en) * | 2003-06-30 | 2004-02-04 | 孙宝远 | Method for producing calcium formate |
| CN1651373A (en) * | 2004-12-03 | 2005-08-10 | 王永军 | Production technology of tetramethylol methane by using ealcium method |
Non-Patent Citations (2)
| Title |
|---|
| 单、双、三季戊四醇的合成. 贺楚华等.化工时刊，第19卷第1期. 2005 * |
| 季戊四醇生产工艺的优化. 王根等.河南化工，第12期. 2000 * |
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