CN1590358A - Process for preparing calcium carboxylate - Google Patents
Process for preparing calcium carboxylate Download PDFInfo
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- CN1590358A CN1590358A CN 03125521 CN03125521A CN1590358A CN 1590358 A CN1590358 A CN 1590358A CN 03125521 CN03125521 CN 03125521 CN 03125521 A CN03125521 A CN 03125521A CN 1590358 A CN1590358 A CN 1590358A
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Abstract
A process for preparing calcium carboxylate features that nitrile compound, the calcium compound chosen from calcium hydroxide, calcium oxide and their mixture, and water take part in reaction at 90-250 deg.C under sufficient pressure.
Description
Related application
The application requires on June 27th, 2002 to submit to, and denomination of invention is the right of priority of the series number of provisional application formerly 60/392,323 of " method for preparing calcium carboxylates ", and it is incorporated herein by the application's reference.
Background of invention
The present invention relates to a kind of use calcium hydroxide or calcium oxide and water, prepare the method for calcium carboxylates by nitrile compound.Aspect one, the present invention relates to prepare the method for calcium propionate by propionitrile and calcium hydroxide or calcium oxide.
Calcium carboxylates prepared according to the methods of the invention can be used for preparing corresponding carboxylic acid.Calcium carboxylates also has other purposes, for example, lime acetate can be used as thickening material, as be used for cake paste, pudding and cake filling, buffer reagent as control food pH in each stage of the course of processing and the finished product, be used to prevent microorganism growth as sanitas, and as the calcium additive of pet products.In addition, calcium propionate is used in the food, particularly baked food with mould fungus inhibition and other microorganisms in large quantities as sanitas, and is used for animal-derived food product as sanitas and nutritional additive.
Calcium carboxylates normally prepares with the method for traditional synthesis of carboxylic acid salt, for example by carbonate, oxyhydroxide or oxide compound and dense or rare carboxylic acid reaction are prepared.Calcium propionate is normally prepared by propionic acid and calcium hydroxide.
United States Patent (USP) 4,700,000 (people such as Merkel) discloses a kind of to prepared the improvement of the traditional method of calcium propionate by propionic acid.People such as Merkel propose, and the water that forms in calcium hydroxide and propionic acid reaction process can be used as the azeotropic mixture of water and propionic acid and removes.People such as Merkel also propose, the gas phase mixture of water and propionic acid can be advantageously used in the preparation calcium propionate, this mixture feeds and contains in the aqueous mixture of calcium propionate and calcium hydroxide in the method, can contain or not contain propionic acid in the described aqueous mixture, in the feeding process, by further adding calcium hydroxide pH regulator is arrived 5-10, and go out calcium propionate by Crystallization Separation.
United States Patent (USP) 3,876,691 (Lincoln) disclose a kind of with the method for baryta water hydrolysis nitrile preparation with the barium salt of the corresponding carboxylic acid of nitrile.But, Lincoln proposes, and calcium oxide is invalid as hydrolytic reagent, and with the most general alkaline earth metal hydroxides of another kind, be that calcium hydroxide is compared, hydrated barta is unique (referring to the EXAMPLE III of Lincoln) with regard to the ability of its hydrolysis nitrile.
United States Patent (USP) 5,763,652 (people such as Kawabe) disclose the method that forms the salt of carboxylic acid and alkali with basic catalyst hydrolysis nitrile compound, and wherein basic catalyst is in particular alkali metal hydroxide (the 3rd hurdle 4-6 is capable).People such as Kawabe disclose also that the nitrile compound hydration is the method for corresponding amides in the presence of manganese oxide catalyst.Randomly, the hydration of nitrile compound can manganese oxide and metal simple-substance or contain Ia family element (as Na, K etc.), IIa family element (as Mg, Ca, Ba etc.), IIb family element (as Zn), IVa elements (as Zr etc.), IVb family element (as Sn etc.), and Va elements (as V etc.) combination of compounds in the presence of carry out (capable) referring to the 12nd hurdle 26-65.People such as Kawabe also propose, the amide compound that the nitrile compound hydration forms can be used the mineral alkali hydrolysis, as alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, alkaline earth metal hydroxides and alkaline earth metal carbonate, preferred alkali metal hydroxide and carbonate (referring to the 15th hurdle 47-57 capable and the 16th hurdle 1-6 is capable).People such as Kawabe had not both openly used calcium hydroxide hydrolysis nitrile compound, and were not open only with calcium cpd hydrolysis nitrile compound yet.
Therefore, in order to prepare calcium propionate from propionitrile, those of ordinary skills will at first can be converted into free acid to propionitrile by acidity or alkaline hydrolysis.Acidic hydrolysis will produce a large amount of ammonium salt by products.Typically use caustic soda.Be that the alkaline hydrolysis meeting that sodium hydroxide carries out consumes a large amount of sodium hydroxide, or need capital-intensive electrodialysis, need then with acid and calcium hydroxide or calcium oxide reaction to prepare calcium propionate to reclaim sodium hydroxide.In addition, those of ordinary skills may use manganese oxide catalyst hydration nitrile compound to form the corresponding amide compound by the guidance of the patent of Kawabe etc., use alkali then.As this amide compound of calcium hydroxide hydrolysis.
So just obtain a kind of method that directly prepares calcium carboxylates of viable commercial from nitrile compound and calcium cpd.
The invention summary
Bright according to this, a kind of method for preparing calcium carboxylates is provided, and it comprises nitrile compound, is selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water be about 90 ℃ to about 250 ℃ in temperature, enough pressure down contact time enough contains the reaction mixture of calcium carboxylates with preparation.
In addition, according to the present invention, from reaction mixture, remove deammoniation and reclaim calcium carboxylates.
In addition, according to the present invention, a kind of method for preparing calcium carboxylates is provided, it comprises that (a) is with nitrile compound, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water in reaction vessel, about 90 ℃ to about 250 ℃ temperature, enough pressure down the contact time enough with preparation contain calcium carboxylates, with first reaction mixture of nitrile compound corresponding amide, calcium hydroxide, water and ammonia; (b) through or without the empty reaction vessel of cold type in advance to remove deammoniation and to obtain second reaction mixture; (c) the optional water that in second reaction mixture, adds in addition; (d) second reaction mixture is heated to proper temperature and reaches, randomly, also remove and anhydrate, and be hydrolyzed into the small part acid amides to obtain extra calcium carboxylates from second reaction mixture, to remove other ammonia; And
(e) reclaim calcium carboxylates.
The accompanying drawing summary
Inapplicable
Detailed Description Of The Invention
The invention provides calcium cpd that a kind of use is selected from calcium hydroxide, calcium oxide or its mixture is directly prepared calcium carboxylates by nitrile compound method, prerequisite is can to carry out under the condition as the manganese oxide catalyst existence there not being independently catalyzer when using calcium cpd hydrolysis nitrile compound.
First embodiment of the present invention relates to the method for preparing calcium carboxylates, it comprises nitrile compound, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water be about 90 ℃ to about 250 ℃ in temperature, enough pressure, the pressure that promptly is enough to reach temperature required contacts time enough contains calcium carboxylates with preparation reaction mixture down.
After formation contained the reaction mixture of calcium carboxylates, reaction mixture was further processed usually to remove deammoniation and reclaim calcium carboxylates from reaction mixture.
Second embodiment of the present invention relates to the preferred method for preparing calcium carboxylates, it comprises: (a) with nitrile compound, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water in reaction vessel, about 90 ℃ to about 250 ℃ temperature, the pressure that enough pressure promptly is enough to reach temperature required down the contact time enough with preparation contain calcium carboxylates, with first reaction mixture of nitrile compound corresponding amide, calcium hydroxide, water and ammonia; (b) optional cooling first reaction mixture, (c) the emptying reaction vessel is to remove deammoniation and to obtain second reaction mixture; (d) the optional water that in second reaction mixture, adds in addition; (e) second reaction mixture is heated to proper temperature and reaches, randomly, also remove and anhydrate, and be hydrolyzed into the small part acid amides to obtain extra calcium carboxylates from second reaction mixture, to remove other ammonia; Reach and (f) reclaim calcium carboxylates.
Can be used for nitrile compound of the present invention and comprise that wherein R is selected from aliphatic group by the nitrile compound of formula R-CN representative, alicyclic hydrocarbon radical, aryl radical, or heterocycle alkyl, wherein R is optional is substituted.
Aliphatic group includes, but are not limited to, and contains 1-12 the carbon atom of having an appointment, the saturated hydrocarbyl of preferred about 1-6 carbon atom, or contain 2-12 the carbon atom of having an appointment, the unsaturated alkyl of preferably about 2-6 carbon atom, the example of the saturated fatty alkyl that is fit to comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl etc.The example of the unsaturated aliphatic hydrocarbyl moiety that is fit to comprises vinyl, allyl group, 1-propenyl, pseudoallyl, crotyl, ethynyl, 2-propynyl etc.
Alicyclic hydrocarbon radical includes, but are not limited to, and contains the cycloalkyl and the cycloalkenyl group of 3-10 the carbon atom of having an appointment.The example of the alicyclic hydrocarbon radical that is fit to comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, the ring octyl group and with the corresponding cycloalkenyl group of these cycloalkyl.
Aryl radical includes, but are not limited to, and contains the aryl and the alkaryl and the aralkyl that contain 7-15 the carbon atom of having an appointment of 6-14 the carbon atom of having an appointment.The example of the aryl radical that is fit to comprises phenyl, naphthyl, phenmethyl, styroyl, tolyl, xylyl etc.
Heterocyclic radical comprises that containing at least one separately is selected from nitrogen-atoms, Sauerstoffatom, or the atom of sulphur atom is as heteroatomic heterocyclic radical, and it can be fragrant heterocyclic radical, nonaromatic heterocycles base, or any in the fused heterocycle base.The example of the heterocyclic radical that is fit to comprises furyl, thienyl, pyrryl, imidazolyl, pyrrolidyl, pyridyl, pyrazinyl, pyrimidyl, indyl, pyridazinyl, piperidino-(1-position only), morpholino, morpholinyl, quinolyl etc.
These groups of being represented by R can be chosen wantonly and be substituted.The substituent example that is fit to comprises halogen atom, hydroxyl, alkyl (as methyl, ethyl, propyl group, sec.-propyl and other C
1-6Alkyl), and aryl (as phenyl, tolyl, xylyl, chloro-phenyl-, p-methoxy-phenyl, naphthyl and other C
6-14Aryl), ether, alkoxyl group (as methoxyl group, oxyethyl group and other C
1-5Alkoxyl group), aryloxy is (as phenoxy group and other C
6-14Aryloxy), sulfydryl, alkylthio (as methylthio group, ethylmercapto group and other C
1-5Alkylthio), arylthio is (as thiophenyl and other C
6-14Arylthio), carboxyl, ester group is (as methoxycarbonyl and other C
1-6Alkoxy carbonyl), acetoxyl group and other C
2-12Acyloxy, and acyl group (as ethanoyl, benzoyl and other C
2-12Acyl group), amino, comprise list or disubstituted amido (as methylamino-, single or two C of dimethylamino and other
1-5Alkylamino), nitro etc.This substituent number that replaces on represented R base can be about 1-4.
The example of suitable fatty nitrile comprises acetonitrile, propionitrile, butyronitrile, isopropyl cyanide nitrile, valeronitrile, isovaleronitrile, own nitrile and other saturated mono nitriles; Propane dinitrile, succinonitrile, trimethylene cyanide, adiponitrile, alpha-amino group propionitrile, alpha-amino group first sulfo-butyronitrile, alpha-amino group butyronitrile, aminoacetonitriles; Lactonitrile, hydroxyacetonitrile, Alpha-hydroxy isopropyl cyanide (ethanoyl cyanalcohol), Alpha-hydroxy-γ-methylthio group butyronitrile (4-methylthio group-2-hydroxybutyronitrile); Cyanoacetic acid; Amino-3-propionitrile, and unsaturated nitrile (as vinyl cyanide, methacrylonitrile, allyl cyanide, crotononitrile) etc.
The example of suitable alicyclic ring nitrile comprises pentamethylene nitrile, cyclohexane nitrile etc.
The example of suitable fragrant nitrile comprises benzonitrile, adjacent-,-with to the benzyl chloride nitrile, adjacent-,-with to the fluorine benzonitrile, adjacent-,-and p-Nitrobenzyl Cyanide, to aminobenzonitrile, the 4-cyanophenol, adjacent-,-and p-tolunitrile, 2, the 4-dichloro-benzonitrile, 2,6-dichloro-benzonitrile, 2,6-difluoro benzonitrile, aubepine nitrile, α-naphthyl cyanide, β-naphthyl cyanide, phthalonitrile, Isophthalodinitrile, para-Phthalonitrile, benzyl cyanide, cinnamyl nitrile, phenylacetonitrile, mandelonitrile, p-hydroxybenzylcyanide, para hydroxybenzene propionitrile, PARA METHOXY PHENYL ACETONITRILE etc.
The example of suitable heterocycle nitrile comprises having the heterocyclic radical that contains 5-or 6-unit ring separately and have at least one atom that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom as heteroatomic nitrile compound, such as the 2-nitrilthiophene, 2-furans nitrile, the 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, cyanopyrazine, the 5-cyanoindole, cyano group piperidines, cyano group piperazine etc.
More specifically, wherein have substituent nitrile compound on the aliphatic group of representing by R, alicyclic hydrocarbon radical, aryl radical or the heterocyclic radical and comprise amino-nitrile compound, cyanohydrin compound etc.The example of nitrogen base nitrile compound comprises aminoacetonitriles, alpha-amino group propionitrile, alpha-amino group butyronitrile, 3-aminopropionitrile etc.The example of cyanohydrin compound comprises α-cyanohydrin compound, β-cyanohydrin compound, γ-cyanohydrin compound etc.This cyanohydrin compound can comprise, and 2-18 according to appointment, preferably about 3-12 is individual, more preferably from about 3-8 carbon atom.
Suitable α-cyanohydrin compound can be expressed from the next:
Wherein, R
1And R
2Represent that independently hydrogen atom maybe can contain substituent alkyl, and R
1And R
2Can form ring with contiguous carbon atom, prerequisite is R
1And R
2Be not hydrogen atom simultaneously.
By R
1, R
2The alkyl of expression, and the substituent example that can have on the alkyl comprises aliphatic group, alicyclic hydrocarbon radical, aryl radical, the substituting group that can have on these groups is with above described consistent for radicals R.
By R
1And R
2Example with the contiguous formed ring of carbon atom comprises cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group etc.
The example of suitable α-cyanohydrin compound comprises hydroxyacetonitrile, lactonitrile, acetone cyanohydrin, 2-hydroxybutyronitrile, 2-hydroxy-4-methyl sulfo-butyronitrile, 2-hydroxy-2-methyl butyronitrile, 2-hydroxy-3-methyl butyronitrile, 2-hydroxyl-3-butyronitrile, 2-hydroxyl valeronitrile, the own nitrile of 2-hydroxyl, 2-hydroxyl caprylic nitrile, and other aliphatic alpha-cyanalcohols; 2-hydroxyl hexanaphthene acetonitrile, cyclopentanone cyanalcohol, pimelinketone cyanalcohol, mandelonitrile, 2-hydroxyl-3-phenylbutyronitrile etc.
The example of suitable β-cyanohydrin compound comprises the 3-hydroxypropionitrile, 3-hydroxybutyronitrile, the own nitrile of 3-hydroxyl, 2-hydroxyl-cyclohexanenitrile or 3-hydroxyl 3-phenyl propionitrile.
The example of suitable γ-cyanohydrin compound comprises 4-hydroxyl-butyronitrile, the own nitrile of 4-hydroxyl, the own nitrile of 3-hydroxyl, 4-hydroxy-4-phenyl butyronitrile etc.
Nitrile compound is preferably such compound, and wherein its corresponding carboxylic acid salt is water miscible.Usually preferred nitrile is a propionitrile, and the by product that it can be used as the adiponitrile preparation process obtains, and preferred calcium carboxylates is a calcium propionate.
Above-mentioned nitrile compound can be by any traditional method preparation well known by persons skilled in the art.For example, fatty nitrile can make by the reaction of haloalkane and sodium cyanide or other alkali metal prussiate.The fragrance nitrile can pass through, and for example, comprises the method preparation of following steps: with amine diazotization and make products therefrom and cuprous cyanide (I) reacts, perhaps also can pass through other path of preparing.Benzonitrile for example, can react in the presence of metal catalyst by phenylformic acid and urea and prepares.In these nitrile compounds, α-cyanohydrin compound can pass through, and for example, comprises the method that makes prussiate and aldehydes or ketones react, comprise order derived from the adducts of aldehydes or ketones and sodium bisulfite and the method for alkali metal cyanide such as potassium cyanide reaction, or the additive method preparation.β-cyanohydrin compound can pass through, and for example, makes the reaction of epoxide and prussic acid make.
The method according to this invention, spendable calcium cpd is selected from calcium hydroxide, calcium oxide, or its mixture.When using calcium oxide, reaction conditions should make at least that partial oxidation calcium can be hydrolyzed to calcium hydroxide.
The amount of the calcium cpd that uses in the inventive method is usually available to join in the reaction vessel mol ratio of calcium cpd and nitrile compound and represents.Widely, the mol ratio of calcium cpd and nitrile compound is about 0.5: 1 to about 0.75: 1.Preferably use with nitrile compound and compare the excessive calcium cpd of stoichiometric ratio, promptly mol ratio will make calcium cpd excessive greater than 0.5: 1.For example, mol ratio is to be equivalent to molar excess 50% at 0.75: 1.The mol ratio of calcium cpd and nitrile compound is preferably greater than 0.5: 1 to about 0.6: 1 (calcium cpd excessive be up to about 20% molar excess), most preferably from about 0.505: 1 to about 0.55: 1 (the about 1%-10% of molar excess).
The water yield of using in the inventive method adds the water yield that is used as reaction solvent/thinner for carrying out the needed amount of this method as the required water yield of hydrolysis.The water yield of using in the inventive method can be represented with joining the water in the reaction vessel and the mol ratio of nitrile compound usually.The mol ratio of water and nitrile compound is about 5: 1 to about 30: 1, preferred about 8: 1 to about 18: 1, and more preferably from about 12: 1 to about 15: 1.
Under the situation that nitrile compound can not fully be dissolved in the water, cosolvent can be used for improving the solubleness of nitrile compound and improve technological operation.Suitable cosolvent comprises water miscible organic solvent, as acetone and other ketone; Methyl alcohol, ethanol and other alcohol; And ethylene glycol, glycerine and other polyvalent alcohols; Dme, tetrahydrofuran (THF), dioxane and other ether.Polyvalent alcohol can also help the carrying out that react by the solubleness that increases calcium hydroxide.Method of the present invention generally can be carried out under about 90 ℃-Yue 250 ℃ temperature of reaction, and preferred about 120 ℃-Yue 250 ℃, more preferably from about 160 ℃-Yue 220 ℃.According to the temperature of reaction and the method that is used for removing from reaction mixture ammonia of hope, method of the present invention can be carried out under any suitable pressure.In order to keep most of water and nitrile compound to be in the liquid phase, preferred usually under temperature of reaction autogenous pressure or above pressure under react.To those skilled in the art, under the situation of not testing too much, just can draw this pressure at an easy rate.For example, when propionitrile as nitrile compound, when temperature of reaction was 170 ℃, autogenous pressure was about 110-120psia (about 758.4-827.4KPa).If will in reaction process, remove deammoniation.As in the process that forms calcium carboxylates, removing deammoniation continuously.Then pressure is preferably autogenous pressure or more than the autogenous pressure, still also can uses the following pressure of autogenous pressure.If the pressure that uses is lower than autogenous pressure,, preferably reclaim any nitrile compound of removing with ammonia and with its recycle then for the optimum operation of the inventive method.Reaction times will be for being suitable for obtaining the time of required nitrile compound to the calcium carboxylates conversion.In general, the reaction times will be along with processing parameter, comprises temperature of reaction and employed nitrile and changes.According to the scale of method and the capital investment of needs, method of the present invention can be carried out with intermittence, semi-batch or continuous mode.
After finishing initial reaction, promptly obtain containing after the reaction mixture of calcium carboxylates, this method comprises further that also recovery and preparation are suitable for commercial calcium carboxylates product.If part as reclaiming technology in reaction process, that is, does not have in the production process of first reaction mixture fully to remove ammonia, will need to remove deammoniation.
The removal of ammonia can be undertaken by any universal method known to a person of ordinary skill in the art.A kind of selection that is used to remove ammonia is that the preparation at first reaction mixture finishes back emptying reaction vessel vapor space.According to the temperature and pressure of first reaction, estimate that this emptying schedule of operation will remove major part usually, i.e. the free ammonia of 55-95%.Second kind of selection is first reaction mixture to be cooled to be lower than under the temperature of atmospheric boiling point before emptying reaction vessel headspace, is usually less than 70 ℃.When if the equipment structure that uses in first reaction is unsuitable for removing ammonia, preferred this selection usually.Behind the emptying EO, pressure that can be by behind evacuation step, promptly preferably under atmospheric pressure or near the normal atmosphere heating second reaction mixture to distill out ammonia and to remove remaining ammonia from cat head.The temperature that the heating of second reaction mixture is reached can be any suitable temperature of removing desired ammonia amount effectively, and this temperature is easy to obtain to those skilled in the art.Usually, this temperature is about 70 ℃ to about 105 ℃.Directly receive distillation if use, promptly do not have distillment rectifying, may must vaporize a large amount of water ammonia is removed to low-down amount at cat head.Anhydrate if will remove, preferably after evacuation step, before the distillation water is joined in the middle of the reaction mixture usually from cat head.If the use cosolvent, and the boiling point of cosolvent makes cosolvent also can remove in still-process, may must be added back to a certain amount of cosolvent in the reaction mixture.Carry out in the presence of excessive calcium cpd if this distillation removes the method for deammoniation, then can promote the hydrolysis of any remaining acid amides suitable with nitrile compound.This distillatory time cycle can be set according to acid amides amount required in distillation condition and the calcium carboxylates product and remaining ammonia amount, and will be conspicuous for those of ordinary skills.
After the removal of ammonia finishes, may adjust the concentration of calcium carboxylates product according to the water yield of having removed in the still-process of removing ammonia (might also have cosolvent).Particularly insoluble excessive calcium cpd all is in the solution in order to ensure all calcium carboxylates, if will may need to carry out the adjusting of concentration subsequently by removing by filter.In addition, if final product will be a solution, regulating concentration is the usually preferred aspect of present method.
After having removed ammonia and having carried out concentration adjustment, the neutralized reaction product mixture is also chosen filtration/separation wantonly.Neutralization (pH regulator) and filtration/separation step can be undertaken by any general technology known to a person of ordinary skill in the art.The quality that concrete neutralization of using and filtration/separation step will depend on used starting raw material, the foreign matter content in the final product, and required quality product.Three kinds of possible selections are below described.
If wish the calcium carboxylates product of extra best best, usually with preferred first kind of selection.In this selection scheme, removing ammonia and carrying out the concentration adjustment step to remove excessive insoluble calcium compound, anyly may be adsorbed onto any other insolubles that exists in other impurity on the particle surface and the used calcium cpd, after insoluble magnesium salts, polymkeric substance of in reaction process, forming etc., use general equipment and technology with the reactive material filtration/separation.After the filtration/separation step, use and the calcium carboxylates corresponding carboxylic acid is regulated pH so as in and dissolved calcium cpd (forming other calcium carboxylates) and make product reach required pH.
If wish to keep the raw material of excessive calcium cpd to be worth, usually with preferred second kind of selection.In this is selected, use with the calcium carboxylates corresponding carboxylic acid in and the excessive calcium cpd that exists.But when using this selection scheme, the impurity of any absorption may be dissolved in the product again.Subsequently in and product carry out filtration/separation to remove residual insolubles.
Require when not too high when preparing solid-state final product and quality product, the third selection is practicable.In this selection, do not carry out the filtration/separation step.Removing ammonia and carrying out the resulting product of the concentration adjustment step excessive calcium cpd that exists with neutralization with the neutralization of calcium carboxylates corresponding carboxylic acid.
Usually preferred first kind of selection and second kind of selection.
In case carried out any filtration/separation and neutralization operation, the calcium carboxylates product after then will filtering and neutralize carries out final product processing, and this depends on the form of required final product, that is, be solution product or solid product.
For solution product, then filter and neutralize after the calcium carboxylates product optionally its concentration is regulated by adding entry or calcium carboxylates, and product store or packing before can use fine filter or suitable separating device to carry out final filtration.
For solid product, then filter and neutralize after the calcium carboxylates product to reclaim and dry.Recovery and drying can use any method in common known to a person of ordinary skill in the art to finish.A kind of selection is to use spray-dryer or by dried particles being sprayed in the fluidized bed dryer and with solution convection drying powdered.Second kind of selection is to collect with the crystallization of calcium carboxylates product, on strainer or whizzer and carry out final drying being used for any general solids dryer of dry wet solid by vaporize water.Usually preferred first kind of selection is unless product quality specifications requires second kind of selection, because second kind of selection will need recycle or dispose the mother liquor logistics.
Embodiment
Embodiment 1
With propionitrile (22 grams, 0.4 the mole, provide by Aldrich Chemical, 97%min), calcium hydroxide (23.2 the gram, 0.31 mole, calibrating level is provided by Fisher Scientific) and deionized water (81.7 grams, 4.54 moles) join in 350 milliliters the autoclave of making by 316 stainless steels, the sealing autoclave, start stirring, and this unit is pressurized to 106psig (730.8KPa), form the helium flow of 30 standard cubic centimeters per minute by headspace with helium.In 0.5 hour, the material in the autoclave is heated to 161 ℃ with electric mantle, then the temperature in the autoclave is controlled at 160 ℃-161 ℃, pressure in the autoclave maintains 127～142psig (979KPa) simultaneously, after 1 hour, under 161 ℃, leave the ammonia in the gas of autoclave with warm pH detection paper.6.8 after hour, stop heating, still can detect in leaving the gas of autoclave and have ammonia this moment.With the autoclave cool overnight, open second day morning.Include a kind of white slurries in the autoclave, very strong ammonia flavor is arranged.Take out the reaction mixture sample, deionized water dilution with 17.3 times, and analyze with the Thermo Separation HPLC of the Hypersil 5 μ C18-BDS posts that 250 * 4.60mm is housed, moving phase is made up of 0.2% phosphate aqueous solution of 5% methyl alcohol and equal amount.Flow velocity is 1 ml/min, flows 12 minutes.The UV-detector that use is operated under 215 λ is carried out quantitatively calcium propionate and propionic acid amide, uses refractive index detector that propionitrile is carried out quantitatively.Find that the reactor product that dilutes comprises 24.2% calcium propionate, the 114ppm propionic acid amide does not detect propionitrile.
Embodiment 2
With propionitrile (413 grams, 7.5 mole, provide by Solutia Inc., refining back: 99.6%min) join in 1 gallon the autoclave of making by 316 stainless steels by funnel, calcium hydroxide (305.7 grams, 4.13 mole, by Mississippi Lime, CODEX Hydrated Lime provides) and half (total deionized water=1835 grams of total deionized water, 101.9 mole) mixing forms slurries and joins in the autoclave by identical funnel, remaining deionized water is used for washing the container of calcium hydroxide slurry and joins autoclave by funnel.Seal autoclave and arrive 50-60psig (344.7-413.7KPa) by nitrogen pressure, pressure relief repeats twice to this step again, thereby air is purged away from system.Pressure controlled valve is set to 150psig (1034.2KPa), and starting is by the nitrogen gas stream (200 standard cubic centimeters per minute) in reactor vapor territory.Start autoclave stirrer and under inner coil pipe pressure the mixture with steam and water material is heated to 170 ℃.In case the autoclave temperature inside reaches 170 ℃,, turn off steam afterwards even reaction was carried out 12.33 hours.Material temperature is reduced to after 60 ℃ in autoclave, and pressure slowly is emptied to barometric point.Then the product slurry is entered in 1 gallon the bottle (2380.4 gram).Analyze slurry by embodiment 1 described HPLC method, find that it comprises 31.0% calcium propionate (quantitative yield in analysis precision), the 431ppm propionic acid amide, and do not detect propionitrile.
Product is removed by filter insoluble calcium hydroxide, obtain 2211 gram filtrates.Most of ammonia are removed by rotatory evaporator under the bath temperature of the pressure that is produced by water aspirator and 60 ℃.In the stripping process intermediate product of ammonia, add the deionized water of about 400 grams so that calcium propionate is retained in the solution.In order to remove the most of remaining propionic acid amide of last Trace Ammonia and hydrolysis, add 300 gram deionized waters and 1.0 gram calcium hydroxides in addition.By being that about 300 gram water and ammonia are removed in air distillation under 103 ℃ the condition in final reference temperature.Adding entry is in order to dissolve all calcium propionates.This solution filtration is obtained 2466 gram solution, wherein comprise 29.3% calcium propionate (quantitative yield in analysis precision), the 112ppm propionic acid amide, and do not detect ammonia.The similar material of this material and other twice hydrolysis reaction is merged, (provide by Aldrich, 99%min) with the pH regulator to 8.1 of merging solution with propionic acid.Remove about 20% water by air distillation and obtain a kind of slurries, on rotatory evaporator from wherein removing most water.Wet solid in vacuum oven dry 24 hours, obtains the exsiccant white solid under 60 ℃, the condition of 12mmHg.This material is chemically examined, and is 90.6% calcium propionate, 9.1% water and the propionic acid amide of 200ppm.
Embodiment 3
With propionitrile (311.5 grams, 5.66 mole, provide by Solutia Inc., refining back: 99.6%min) join in 1 gallon the autoclave of making by 316 stainless steels by funnel, calcium hydroxide (229.3 the gram, 3.09 moles, by Mississippi Lime, CODEX Hydrated Lime provides) and deionized water (1007.2 gram, 55.9 moles) mix and form slurries and join in the autoclave by identical funnel.Second section deionized water (345.1 grams, 19.2 moles) is used for washing the container of calcium hydroxide slurry and joins autoclave by funnel.With nitrogen autoclave is pressurized to 45-55psig (310.3-379.2KPa), pressure is reduced to 25psig (172.4KPa), this step repeats twice again, thereby most air is purged away from system.Pressure controlled valve is set to 260psig (1792.6KPa), and starting is by the nitrogen gas stream (100 standard cubic centimeters per minute) in reactor vapor territory.Start autoclave stirrer and under inner coil pipe pressure the mixture with steam and water material is heated to 200 ℃.Material temperature reached 200 ℃ after 1 hour in autoclave, and nitrogen gas stream is increased to 200 cc/min to improve the control of autoclave pressure.Material temperature reaches 200 ℃ altogether after 2 hours in autoclave, steam off, and by being heated to the steam-pipe releasing reactor pressure in 40 minutes time more than 200 ℃.Water that flash distillation is come out from autoclave and ammonia are collected by entering a washer that contains 4862.6 gram frozen water.After autoclave pressure had all discharged, scrubber liquor weighed 5414.9 grams.After material temperature in the autoclave is reduced to below 60 ℃, with its discharge and weigh (925.1 gram).Add deionized water (237.2 gram) to dissolve all calcium propionates.By the product of embodiment 1 described HPLC method analysis dilution, find that it comprises 28.0% calcium propionate (326 grams, 1.75 moles, yield 62%), the 119ppm propionic acid amide, and do not detect propionitrile.Find to comprise in the scrubber liquor ammonia of 0.34% calcium propionate and 1.58%.The amount of calcium propionate can draw from washer, and nearly 66.4 gram products have been by having been taken in the washer by carrying secretly, and has 400 gram water and 85.5 gram ammonia flash distillations from autoclave to come out, and this accounts for 90% of the propionitrile ammonia that complete hydrolysis discharges that is fed in the autoclave.After discharging, do not attempt product calcium propionate amount remaining in the quantitative assay reactor.
Embodiment 4
With calcium hydroxide (23.4 grams, 0.316 mole, by Mississippi Lime, CODEX HydratedLime provides) deionized water (148 the gram, 8.2 mole) slurries join in 300 milliliters the Hastelloy autoclave that the water cooling reflux exchanger is housed, and with nitrogen autoclave are pressurized to 235psig (1620.3KPa), pressure are reduced to 10psig (68.9KPa) again, this circulation repeats twice again, thereby most air is purged away from system.Then autoclave is pressurized to 235psig (1620.3KPa), and form the stable nitrogen gas stream of 50 standard cubic centimeters per minute at the top of reflux exchanger, after material is heated to 200 ℃ in autoclave, in 2 hours, inject (43.3 milliliters of propionitrile by high pressure syringe pump, 33.8 gram, 0.615 mole is provided by Solutia Inc., refining back: 99.6%min).Leave unitary gas by water scrubber to catch any propionitrile, ammonia and the water of from autoclave, discharging.After the reinforced end of propionitrile, take out material sample in the reactor, get one again after 1 hour and 2 hours then.Water in the gas scrubber is also discharged, is weighed, and replaces with fresh deionized water when taking out each sample.By propionitrile, propionic acid amide and the calcium propionate content in material and the washer sample in the embodiment 1 described HPLC method analysis reactor, do not have calcium propionate or propionic acid amide in the washer sample, this shows that liquid material in the autoclave does not take place is entrained to phenomenon in the gas.Also carry out titration and detect ammonia in the washer sample by hydrochloric acid with 0.1N.From these data, can calculate the percentage ratio of propionitrile in the following gas, propionic acid amide, calcium propionate and leave the propionitrile of autoclave and the timetable of the mole number of ammonia.These the results are shown in the following table:
| Time (hour) | Propionitrile (wt%) | Propionic acid amide (wt%) | Calcium propionate (wt%) | Propionitrile (mole) | Ammonia (mole) |
| ?2 | ??1.06％ | ?0.35％ | ?26.1％ | ??0.0001 | ??0.0012 |
| ?3 | ??0.00％ | ?0.13％ | ?26.9％ | ??0.0000 | ??0.0148 |
| ?4 | ??0.00％ | ?0.08％ | ?27.35％ | ??0.0000 | ??0.0116 |
Claims (40)
1. method for preparing calcium carboxylates, it comprises nitrile compound, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water be about 90 ℃ to about 250 ℃ in temperature, enough pressure down contact time enough contains the reaction mixture of calcium carboxylates with preparation.
2. the process of claim 1 wherein that described nitrile compound represents that by formula R-CN wherein R is selected from aliphatic group, alicyclic hydrocarbon radical, aryl radical, or heterocycle alkyl, and wherein R is optional is substituted.
3. the method for claim 2, wherein said R is an aliphatic group.
4. the method for claim 3, wherein said nitrile is a propionitrile.
5. the process of claim 1 wherein that the mol ratio of calcium cpd and nitrile compound is about 0.5: about 0.75: 1 of 1-.
6. the method for claim 5, wherein the mol ratio of calcium cpd and nitrile compound is greater than 0.5: about 0.6: 1 of 1-.
7. the process of claim 1 wherein that the mol ratio of water and nitrile compound is about 5: about 30: 1 of 1-.
8. the method for claim 7, wherein the mol ratio of water and nitrile compound is about 12: about 15: 1 of 1-.
9. the method for claim 1 also comprises and remove deammoniation from described reaction mixture.
10. the method for claim 9 also comprises and reclaims described calcium carboxylates.
11. the process of claim 1 wherein that described temperature is about 160 ℃-Yue 220 ℃.
12. the method for claim 1 also comprises and remove deammoniation from described reaction mixture, and reclaims calcium carboxylates subsequently.
13. a method for preparing calcium carboxylates, it comprises
(a) with nitrile compound, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water in reaction vessel, about 90 ℃ to about 250 ℃ temperature, enough pressure down the contact time enough with preparation contain calcium carboxylates, with first reaction mixture of described nitrile compound corresponding amide, water and ammonia;
(b) optional first reaction mixture is cooled off;
(c) the emptying reaction vessel is to remove deammoniation and to obtain second reaction mixture;
(d) the optional water that in second reaction mixture, adds in addition;
(e) described second reaction mixture is heated to proper temperature and reaches, randomly, also remove and anhydrate, and be hydrolyzed into the described acid amides of small part to obtain extra calcium carboxylates from second reaction mixture, to remove other ammonia; And
(f) reclaim calcium carboxylates.
14. the method for claim 13, wherein said nitrile compound represents that by formula R-CN wherein R is selected from aliphatic group, alicyclic hydrocarbon radical, and aryl radical, or heterocycle alkyl, and wherein R is optional is substituted.
15. the method for claim 14, wherein said R is an aliphatic group.
16. the method for claim 15, wherein said nitrile are propionitrile.
17. the method for claim 13, wherein the mol ratio of calcium cpd and nitrile compound is about 0.5: about 0.75: 1 of 1-.
18. the method for claim 17, wherein the mol ratio of calcium cpd and nitrile compound is greater than 0.5: about 0.6: 1 of 1-.
19. the method for claim 13, wherein the water that adds in the step (a) and the mol ratio of nitrile compound are about 5: about 30: 1 of 1-.
20. the method for claim 19, wherein the water that adds in the step (a) and the mol ratio of nitrile compound are about 12: about 15: 1 of 1-.
21. the method for claim 13, wherein said temperature are about 160 ℃-Yue 220 ℃.
22. the method for claim 13, wherein said calcium carboxylates reclaims by following steps:
(i) concentration of product in the regulating step (e),
(ii) remove by filter insoluble unreacted calcium cpd,
(iii) add with the nitrile compound corresponding carboxylic acid with neutralize any dissolved calcium cpd and generate neutralized reaction product and
(iv) choose wantonly neutralized reaction product is filtered to remove insolubles and to generate the neutral solution product.
23. the method for claim 22 also comprises the solution product drying after the neutralization with preparation solid carboxylic acid calcium.
24. the method for claim 13, wherein said calcium carboxylates reclaims by following steps:
(i) concentration of product in the regulating step (e),
(ii) add with the nitrile compound corresponding carboxylic acid with neutralize remaining calcium cpd and generate neutralized reaction product and
(iii) choose wantonly neutralized reaction product is filtered to remove insolubles and to generate the neutral solution product.
25. the method for claim 24 also comprises the solution product drying after the neutralization with preparation solid carboxylic acid calcium.
26. the method for claim 13 was wherein cooled off described first reaction mixture before the emptying of described step (c).
27. method for preparing calcium carboxylates, it comprises propionitrile, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water about 90 ℃ to about 250 ℃ of temperature, be enough to obtain contact temperature required pressure under time enough contains calcium propionate with preparation reaction mixture; Wherein the mol ratio of calcium cpd and propionitrile is about 0.5: about 0.75: 1 of 1-, the mol ratio of water and propionitrile is about 5: about 30: 1 of 1-.
28. the method for claim 27, wherein the mol ratio of calcium cpd and propionitrile is greater than 0.5: about 0.6: 1 of 1-.
29. the method for claim 27, wherein the mol ratio of water and nitrile compound is about 12: about 15: 1 of 1-.
30. the method for claim 27, wherein said temperature are about 160 ℃-Yue 220 ℃.
31. the method for claim 27 also comprises and remove deammoniation from described reaction mixture.
32. the method for claim 31 also comprises and reclaims described calcium propionate.
33. the method for claim 27 also comprises and removes deammoniation and reclaim calcium propionate subsequently from described reaction mixture.
34. a method for preparing calcium propionate, it comprises
(a) with propionitrile, be selected from the calcium cpd of calcium hydroxide, calcium oxide or its mixture, with water in reaction vessel, about 90 ℃ to about 250 ℃ temperature, enough pressure contact time enough down contains first reaction mixture of calcium propionate, propionic acid amide, water and ammonia with preparation;
(b) optional first reaction mixture is cooled off;
(c) the emptying reaction vessel is to remove deammoniation and to obtain second reaction mixture;
(d) the optional water that in second reaction mixture, adds in addition;
(e) described second reaction mixture is heated to proper temperature and reaches, randomly, also remove and anhydrate, and be hydrolyzed into the described acid amides of small part to obtain extra calcium propionate from second reaction mixture, to remove other ammonia; And
(f) reclaim calcium propionate;
Wherein, the mol ratio of calcium cpd and propionitrile is about 0.5: about 0.75: 1 of 1-, the mol ratio of water and propionitrile is about 5: about 30: 1 of 1-.
35. the method for claim 34, wherein said calcium propionate reclaims by following steps:
(i) concentration of product in the regulating step (e),
(ii) remove by filter insoluble unreacted calcium cpd,
(iii) add propionic acid with neutralize any dissolved calcium cpd and generate neutralized reaction product and
(iv) choose wantonly neutralized reaction product is filtered to remove insolubles and to generate the neutral solution product.
36. the method for claim 35 also comprises the solution product drying after the neutralization with preparation solid calcium propionate.
37. the method for claim 34, wherein said calcium propionate reclaims by following steps:
(i) concentration of product in the regulating step (e),
(ii) add propionic acid with neutralize remaining calcium cpd and generate neutralized reaction product and
(iii) choose wantonly neutralized reaction product is filtered to remove insolubles and to generate the neutral solution product.
38. the method for claim 37 also comprises the solution product drying after the neutralization with preparation solid calcium propionate.
39. the method for claim 34, wherein said temperature are about 160 ℃-Yue 220 ℃.
40. the method for claim 34 was wherein cooled off described first reaction mixture before the emptying of described step (c).
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|---|---|---|---|
| CN 03125521 CN1590358A (en) | 2003-09-01 | 2003-09-01 | Process for preparing calcium carboxylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03125521 CN1590358A (en) | 2003-09-01 | 2003-09-01 | Process for preparing calcium carboxylate |
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