CA2037873A1 - Process for the production of calcium formate and the use of same as feed additive - Google Patents
Process for the production of calcium formate and the use of same as feed additiveInfo
- Publication number
- CA2037873A1 CA2037873A1 CA002037873A CA2037873A CA2037873A1 CA 2037873 A1 CA2037873 A1 CA 2037873A1 CA 002037873 A CA002037873 A CA 002037873A CA 2037873 A CA2037873 A CA 2037873A CA 2037873 A1 CA2037873 A1 CA 2037873A1
- Authority
- CA
- Canada
- Prior art keywords
- formate
- calcium
- reaction
- calcium hydroxide
- calcium formate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 title claims abstract description 36
- 239000004281 calcium formate Substances 0.000 title claims abstract description 36
- 229940044172 calcium formate Drugs 0.000 title claims abstract description 36
- 235000019255 calcium formate Nutrition 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000003674 animal food additive Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 16
- 230000008569 process Effects 0.000 title claims description 16
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 25
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 4
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 abstract description 7
- 150000003077 polyols Chemical class 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 17
- 241001465754 Metazoa Species 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/10—Organic substances
- A23K20/105—Aliphatic or alicyclic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K20/00—Accessory food factors for animal feeding-stuffs
- A23K20/20—Inorganic substances, e.g. oligoelements
- A23K20/24—Compounds of alkaline earth metals, e.g. magnesium
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Food Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Calcium formate can be produced with high space-time yields and low engineering expenditure by reacting methyl formate and calcium hydroxide in a molar ratio of substantially 2:1 in an aqueous suspension at 20 to 100°. At the start of the reaction the weight ratio of calcium hydroxide to water is 1:1 to 1:5. Prior to or upon distilling off the methanol formed, the crystalline calcium formate is separated from the aqueous phase and dried. The calcium formate thus produced is better suited as a feed additive than calcium formate obtained as by-product in the production of polyols.
Calcium formate can be produced with high space-time yields and low engineering expenditure by reacting methyl formate and calcium hydroxide in a molar ratio of substantially 2:1 in an aqueous suspension at 20 to 100°. At the start of the reaction the weight ratio of calcium hydroxide to water is 1:1 to 1:5. Prior to or upon distilling off the methanol formed, the crystalline calcium formate is separated from the aqueous phase and dried. The calcium formate thus produced is better suited as a feed additive than calcium formate obtained as by-product in the production of polyols.
Description
The present invention relates to a process for the production of calcium formate and to its use as a feed additive.
Calcium formate, l.e. the calcium salt of formic acid, is almost exclusively obtained as a by-product in the production of the polyhydric alcohols (polyols) pentaerythrite trimethylolethane, trimethylol propane and neopentyl glycol. It is formed in the reaction of the 3-hydroxyl-aldehyde (obtainable by alcohol condensation) with formaldehyde in the presence of calcium hydroxide and is thus the oxidation product of a mixed Cannizzaro reaction.
Calcium formate is used for various purposes, such as for example, as an aid in tanning, for the production of formic acid, as a setting activator in the cement industry, lS as an ensiling aid and to an increasing extent as a nutritionly effective feed additive in the nutrition of animals.
When calcium formate is used for improving the utilization o~ feeds, for reducing indigestion, for avoiding microbial feed decay (see pamphlet of Degussa AE "Calcium Formate"-CH 609-1-105-988DD), it must satisfy special requirements with regard to quality so that the feed containing calcium formate is not refused by the animals.
Calcium formate from the polyol synthesis contains odor and/or taste intensive impurities whose effect increases with concentration. The highPr the content of these impurities the less the animals will be ready to accept feeds mixed with this kind of calcium formate. A purification of the calcium formate from the polyol synthe~is can actually be carried out, but the costs of the process thus are increased and the economy is reduced.
.
,..:. . .
. .
' ':. . , ' . ~ ' ' - ' . ' ' , .
- . . . . . . : . :
.
, ~ ; : .. .
:
The disadvantage of the production of calcium formate as a by-product of the polyol synthesis lies in the fact that an increase in the production of calcium formate can be attained only with a corresponding increase in the polyol production.
This would require corresponding sales opportunities.
Wet and dry processes for the production of calcium formate by carbonylation of calcium hydroxide are also known (see Gmelin-Handbuch, Volume Ca B, Page 161-162). These processes generally require high pressures, for example, 6-8 MPa, temperatures ranging from 150 to 170C and very long reaction times. Besides the concomitant use of alkali formates or alkali hydroxide in the reaction mixture, the space-time yield can actually be improved and the required pressure can be reduced. However, the required after-purification in order to obtain calcium formate free from alkali is a disadvantage. Furthermore, the equipment for the carbonylation of calcium hydroxide is technologically very expensive.
.
Methyl formate is available in adequate amounts as intermediate product in the production of formic acid.
Methyl formate is obtained by carbonylation of methanol in the presence of sodium methylate as catalyst. Sodium formate can be formed in a side reaction in the presence of moisture -(Ullmann's Encyclopedia, 4th Edition, Vol. A12, Page 19).
The hydrolysis of methyl formate for the production of calcium formate was never considered heretofore.
It is an object of the present invention to provide a process that allows the production of calcium formate by means of a simple reaction from readily available starting materials and with low technological expenditure. The process should result in a high space-time yield and in a calcium formate quality that will be acceptable to animals as a feed additive.
' . ~ , ~ .' ' .- : .
'': ' ', ' . ' . :
.~ ~ ' .. . ' "' ' ' : . '., , '.. ' ' ~ ' . :
.. . . .. . .
' According to the present invention there is provided a process for the production of calcium formate, wherein methyl formate and calcium hydroxide are reacted in a molar ratio of about 2:1 in aqueous suspension at 20 to 100 C, the weight ratio of calcium hydroxide to water is 1:1 to 1:5 at the start of the reaction, and the crystalline calcium formate is separated from the aqueous phase and dried prior to or upon distilling off of the methanol formed in the reaction.
The processs is based on the reaction of methyl formate with calcium hydroxide. The calcium formate produced according to the present invention is more readily accepted by animals as feed additive than the calcium formate obtained as by-product in the production of polyols since it is free from unpleasant impurities that can cause the animals to refuse the feed.
Surprisingly, it has now been found that the reaction of methyl formate and calcium hydroxide in the presence of water proceeds virtually instantaneously, thus resulting in high space-time yields. Because of the enthalpy of reaction liberated during the reaction, the reaction mixture can be heated to the desired temperature. Fundamentally the reaction temperature may be outside the range of 20 to 100C, but this is usually not preferred. Reaction temperatures ranging from approximately 50 to 80C are particularly favourable. As the amounts of water increases in the calcium hydroxide suspension used the resulting reaction temperature decreases. Suspension having a Ca(OH)2 content of 20 to 35%
by weight, particularly 30 to 35% by weight are preferably used.
On carrying out the process discontinuously or continuously, methyl formate which can still contain specific -~
portions of methanol from its production can be brought into contact with the aqueous calcium hydroxide suspension either as a liquid or as a vapour and can then be intensively mixed.
When required not quantitatively reacted methyl formate is condensed and thus is kept available for the reaction.
According to a preferred embodiment a very small calcium hydroxide excess is used and on completion of the reaction the pH is adjusted with methyl formate to a value of between 5 and 7, preferably 6 to 7.
The methanol forming during the reaction can be distilled from the calcium formate-containing reaction lo mixture whilst or after the reactants are brought into contact with each other. The methanol can be distilled off while utilizing the enthalpy of reaction. Alternatively the crystalline calcium formate may also be separated from the aqueous-methanolic, liquid phase by means of solid-liquid separates and methanol can subsequently be received from the liquid phase by distillation. For the separation of the calcium formate from the aqueous or aqueous-methanolic phase continuously or discontinuously operating centrifuges or filtering devices are suitable. The separated calcium formate is dried by using conventional driers.
When carrying out the process continuously according to a preferred embodiment of the present invention methyl formate and an aqueous calcium hydroxide suspension, in a molar ratio of substantially 2:1, are simultaneously fed into a gas-tight reactor. The reaction is then carried out at 40 to 100C, preferably at 50 to 80C, at the resulting pressure practically quantitatively within very short residence times.
A prejudice against the production of calcium formate from a calcium hydroxide and methyl formate was evidently held since the carbonylation of calcium hydroxide was looked upon as the obvious way. It could not be predicted that the reaction of methyl formate with an aqueous calcium hydroxide -., - - .. ~ . .. - : :: . . -. . ..
,: ' , ' -, '. :,.. ': .' ' . ''.: ... '" : : ': , ' :
'' ~ ' : : - : : . . -suspension is practically instantaneous and that it can ~e carried out with a minimum of technological expenditure. ~he calcium formate can thus be obtained in a very economical manner and, in addition, it has the advantage that when using it as a feed additive there exists no risk of acceptance problems.
The process according to the present invention will now be explained in greater detail by means of the examples hereafter.
Example 1 75.5 g (1 mole) of 98% calcium hydroxide are suspended in 200 ml of water. Within 30 minutes 124 g (2 moles) of methyl formate (content 97% the remainder being methanol) are added dropwise. The temperature of the reaction mixtures increases to approximately 70C, the reaction bein~
spontaneous.
When required, non-reacted methyl formate is condensed and thus fed again to the reaction mixture. Upon completed addition of methyl formate the reaction also is terminated.
The pH value is adjusted to 6.5 by adding 0.5 ml of an 85% formic acid. The calcium formate is filtered off from the aqueous~methanolic phase and then dried. The yield is 110 g corresponding to a theoretical yield of 85%. The methanol can be distilled off from the mother li~uor and the aqueous sump that still contains calcium formate is then passed to a subsequent batch for the suspension of calcium hydroxide. In this manner a virtually quantitative yield can be obtained.
Example 2 . . ~ :' ' : . '. .. , ,,- ~ . . :.- . , .. : ... . . . . . .
, ' ' ' , ' , : ' . ',, ', ' ' ~ ' : . ;' ':: ' ' ' , . , ~ . . .
37.8 g (0.5 kmole) of a 98% calcium hydroxide are suspended in 100 ml of water to a dispersion and mixed with 62 kg ( 1 kmole) of a 97% methyl formate within 45 to 60 minutes while stirring well. The boileer is cooled intensively and the temperature in the reaction mixture increases to approximately 80C. Boiling methyl formate is condensed on the cooler. The reaction time is limited by the cooling performance of the plant.
Upon completed addition of the methyl formate the reaction also is practically terminated. 150 to 200 ml of a 85% formic acid are added to the suspension, followed by homogenizing and filtering from the solution. A methanol-free mother liquor from a preceding test was used for washing.
Upon drying there remain 60.5 kg corresponding to a theoretical yield of 93%; purity: > 99%. ;
-. ~ . . : , , .:
. . . . . . - . :.
' ',, ' :.:' . . .:' ' . ' ' : ~ ' ., , . .: : : .
Calcium formate, l.e. the calcium salt of formic acid, is almost exclusively obtained as a by-product in the production of the polyhydric alcohols (polyols) pentaerythrite trimethylolethane, trimethylol propane and neopentyl glycol. It is formed in the reaction of the 3-hydroxyl-aldehyde (obtainable by alcohol condensation) with formaldehyde in the presence of calcium hydroxide and is thus the oxidation product of a mixed Cannizzaro reaction.
Calcium formate is used for various purposes, such as for example, as an aid in tanning, for the production of formic acid, as a setting activator in the cement industry, lS as an ensiling aid and to an increasing extent as a nutritionly effective feed additive in the nutrition of animals.
When calcium formate is used for improving the utilization o~ feeds, for reducing indigestion, for avoiding microbial feed decay (see pamphlet of Degussa AE "Calcium Formate"-CH 609-1-105-988DD), it must satisfy special requirements with regard to quality so that the feed containing calcium formate is not refused by the animals.
Calcium formate from the polyol synthesis contains odor and/or taste intensive impurities whose effect increases with concentration. The highPr the content of these impurities the less the animals will be ready to accept feeds mixed with this kind of calcium formate. A purification of the calcium formate from the polyol synthe~is can actually be carried out, but the costs of the process thus are increased and the economy is reduced.
.
,..:. . .
. .
' ':. . , ' . ~ ' ' - ' . ' ' , .
- . . . . . . : . :
.
, ~ ; : .. .
:
The disadvantage of the production of calcium formate as a by-product of the polyol synthesis lies in the fact that an increase in the production of calcium formate can be attained only with a corresponding increase in the polyol production.
This would require corresponding sales opportunities.
Wet and dry processes for the production of calcium formate by carbonylation of calcium hydroxide are also known (see Gmelin-Handbuch, Volume Ca B, Page 161-162). These processes generally require high pressures, for example, 6-8 MPa, temperatures ranging from 150 to 170C and very long reaction times. Besides the concomitant use of alkali formates or alkali hydroxide in the reaction mixture, the space-time yield can actually be improved and the required pressure can be reduced. However, the required after-purification in order to obtain calcium formate free from alkali is a disadvantage. Furthermore, the equipment for the carbonylation of calcium hydroxide is technologically very expensive.
.
Methyl formate is available in adequate amounts as intermediate product in the production of formic acid.
Methyl formate is obtained by carbonylation of methanol in the presence of sodium methylate as catalyst. Sodium formate can be formed in a side reaction in the presence of moisture -(Ullmann's Encyclopedia, 4th Edition, Vol. A12, Page 19).
The hydrolysis of methyl formate for the production of calcium formate was never considered heretofore.
It is an object of the present invention to provide a process that allows the production of calcium formate by means of a simple reaction from readily available starting materials and with low technological expenditure. The process should result in a high space-time yield and in a calcium formate quality that will be acceptable to animals as a feed additive.
' . ~ , ~ .' ' .- : .
'': ' ', ' . ' . :
.~ ~ ' .. . ' "' ' ' : . '., , '.. ' ' ~ ' . :
.. . . .. . .
' According to the present invention there is provided a process for the production of calcium formate, wherein methyl formate and calcium hydroxide are reacted in a molar ratio of about 2:1 in aqueous suspension at 20 to 100 C, the weight ratio of calcium hydroxide to water is 1:1 to 1:5 at the start of the reaction, and the crystalline calcium formate is separated from the aqueous phase and dried prior to or upon distilling off of the methanol formed in the reaction.
The processs is based on the reaction of methyl formate with calcium hydroxide. The calcium formate produced according to the present invention is more readily accepted by animals as feed additive than the calcium formate obtained as by-product in the production of polyols since it is free from unpleasant impurities that can cause the animals to refuse the feed.
Surprisingly, it has now been found that the reaction of methyl formate and calcium hydroxide in the presence of water proceeds virtually instantaneously, thus resulting in high space-time yields. Because of the enthalpy of reaction liberated during the reaction, the reaction mixture can be heated to the desired temperature. Fundamentally the reaction temperature may be outside the range of 20 to 100C, but this is usually not preferred. Reaction temperatures ranging from approximately 50 to 80C are particularly favourable. As the amounts of water increases in the calcium hydroxide suspension used the resulting reaction temperature decreases. Suspension having a Ca(OH)2 content of 20 to 35%
by weight, particularly 30 to 35% by weight are preferably used.
On carrying out the process discontinuously or continuously, methyl formate which can still contain specific -~
portions of methanol from its production can be brought into contact with the aqueous calcium hydroxide suspension either as a liquid or as a vapour and can then be intensively mixed.
When required not quantitatively reacted methyl formate is condensed and thus is kept available for the reaction.
According to a preferred embodiment a very small calcium hydroxide excess is used and on completion of the reaction the pH is adjusted with methyl formate to a value of between 5 and 7, preferably 6 to 7.
The methanol forming during the reaction can be distilled from the calcium formate-containing reaction lo mixture whilst or after the reactants are brought into contact with each other. The methanol can be distilled off while utilizing the enthalpy of reaction. Alternatively the crystalline calcium formate may also be separated from the aqueous-methanolic, liquid phase by means of solid-liquid separates and methanol can subsequently be received from the liquid phase by distillation. For the separation of the calcium formate from the aqueous or aqueous-methanolic phase continuously or discontinuously operating centrifuges or filtering devices are suitable. The separated calcium formate is dried by using conventional driers.
When carrying out the process continuously according to a preferred embodiment of the present invention methyl formate and an aqueous calcium hydroxide suspension, in a molar ratio of substantially 2:1, are simultaneously fed into a gas-tight reactor. The reaction is then carried out at 40 to 100C, preferably at 50 to 80C, at the resulting pressure practically quantitatively within very short residence times.
A prejudice against the production of calcium formate from a calcium hydroxide and methyl formate was evidently held since the carbonylation of calcium hydroxide was looked upon as the obvious way. It could not be predicted that the reaction of methyl formate with an aqueous calcium hydroxide -., - - .. ~ . .. - : :: . . -. . ..
,: ' , ' -, '. :,.. ': .' ' . ''.: ... '" : : ': , ' :
'' ~ ' : : - : : . . -suspension is practically instantaneous and that it can ~e carried out with a minimum of technological expenditure. ~he calcium formate can thus be obtained in a very economical manner and, in addition, it has the advantage that when using it as a feed additive there exists no risk of acceptance problems.
The process according to the present invention will now be explained in greater detail by means of the examples hereafter.
Example 1 75.5 g (1 mole) of 98% calcium hydroxide are suspended in 200 ml of water. Within 30 minutes 124 g (2 moles) of methyl formate (content 97% the remainder being methanol) are added dropwise. The temperature of the reaction mixtures increases to approximately 70C, the reaction bein~
spontaneous.
When required, non-reacted methyl formate is condensed and thus fed again to the reaction mixture. Upon completed addition of methyl formate the reaction also is terminated.
The pH value is adjusted to 6.5 by adding 0.5 ml of an 85% formic acid. The calcium formate is filtered off from the aqueous~methanolic phase and then dried. The yield is 110 g corresponding to a theoretical yield of 85%. The methanol can be distilled off from the mother li~uor and the aqueous sump that still contains calcium formate is then passed to a subsequent batch for the suspension of calcium hydroxide. In this manner a virtually quantitative yield can be obtained.
Example 2 . . ~ :' ' : . '. .. , ,,- ~ . . :.- . , .. : ... . . . . . .
, ' ' ' , ' , : ' . ',, ', ' ' ~ ' : . ;' ':: ' ' ' , . , ~ . . .
37.8 g (0.5 kmole) of a 98% calcium hydroxide are suspended in 100 ml of water to a dispersion and mixed with 62 kg ( 1 kmole) of a 97% methyl formate within 45 to 60 minutes while stirring well. The boileer is cooled intensively and the temperature in the reaction mixture increases to approximately 80C. Boiling methyl formate is condensed on the cooler. The reaction time is limited by the cooling performance of the plant.
Upon completed addition of the methyl formate the reaction also is practically terminated. 150 to 200 ml of a 85% formic acid are added to the suspension, followed by homogenizing and filtering from the solution. A methanol-free mother liquor from a preceding test was used for washing.
Upon drying there remain 60.5 kg corresponding to a theoretical yield of 93%; purity: > 99%. ;
-. ~ . . : , , .:
. . . . . . - . :.
' ',, ' :.:' . . .:' ' . ' ' : ~ ' ., , . .: : : .
Claims (5)
1. A process for the production of calcium formate, wherein methyl formate and calcium hydroxide are reacted in a molar ratio of about 2:1 in aqueous suspension at 20 to 100°C, the weight ratio of calcium hydroxide to water is 1:1 to 1:5 at the start of the reaction, and the crystalline calcium formate is separated from the aqueous phase and dried prior to or upon distilling off of the methanol formed in the reaction.
2. A process as claimed in claim 1, wherein the aqueous calcium hydroxide suspension contains 20 to 35 % by weight of calcium hydroxide.
3. A process as claimed in claim 1, wherein the reaction is carried out in the presence of a calcium hydroxide excess of up to 5 mole %, and upon completion of the reaction the pH is adjusted to a value of 5 to 7 by the addition of formic acid.
4. A process as in any one of claims 1 to 3, wherein methyl formate and an aqueous suspension of calcium hydroxide are continuously fed into a reactor, and the reaction is carried out at 50 to 60°C and at the resulting pressure.
5. The use of the calcium formate produced by a process as claimed in any one of claims 1 to 4 as a feed additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4007665.2 | 1990-03-10 | ||
| DE4007665A DE4007665C1 (en) | 1990-03-10 | 1990-03-10 | Calcium formate prodn. - by reacting methyl formate and calcium hydroxide in aq. suspension, using specified wt. ratio of calcium hydroxide to water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2037873A1 true CA2037873A1 (en) | 1991-09-11 |
Family
ID=6401903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037873A Abandoned CA2037873A1 (en) | 1990-03-10 | 1991-03-08 | Process for the production of calcium formate and the use of same as feed additive |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA2037873A1 (en) |
| DE (1) | DE4007665C1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248363A (en) * | 2021-05-17 | 2021-08-13 | 岳阳昌德环境科技有限公司 | Recycling method of methyl formate waste liquid |
| CN115636746A (en) * | 2022-10-22 | 2023-01-24 | 新疆至创新材料有限公司 | A high-value comprehensive utilization process of coal-based ethylene glycol methyl formate waste liquid |
| CN116282112A (en) * | 2022-10-22 | 2023-06-23 | 新疆天业（集团）有限公司 | Process for refining low-grade calcium formate and preparing high-purity calcium-based compound based on calcium formate |
-
1990
- 1990-03-10 DE DE4007665A patent/DE4007665C1/en not_active Expired - Lifetime
-
1991
- 1991-03-08 CA CA002037873A patent/CA2037873A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248363A (en) * | 2021-05-17 | 2021-08-13 | 岳阳昌德环境科技有限公司 | Recycling method of methyl formate waste liquid |
| CN115636746A (en) * | 2022-10-22 | 2023-01-24 | 新疆至创新材料有限公司 | A high-value comprehensive utilization process of coal-based ethylene glycol methyl formate waste liquid |
| CN116282112A (en) * | 2022-10-22 | 2023-06-23 | 新疆天业（集团）有限公司 | Process for refining low-grade calcium formate and preparing high-purity calcium-based compound based on calcium formate |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4007665C1 (en) | 1991-09-19 |
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