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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/02—Formic acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
  • C07C53/02—Formic acid
  • C07C53/06—Salts thereof

Definitions

• the invention relates to a process for the production of formic acid formates and the use of the formic acid formates produced thereafter for the preservation and / or acidification of plant and / or animal substances, for the treatment of bio-waste and as an additive in animal nutrition or as a growth promoter for animals.
• Formic acid formates have an antimicrobial effect and are used, for example, for the preservation and acidification of plant and animal substances, such as grasses, agricultural products or meat, for the treatment of bio-waste or as an additive for animal nutrition.
• DE 424 017 describes the preparation of formic acid sodium formates with different acid content by introducing sodium formate into aqueous formic acid in a corresponding molar ratio.
• DE-A 198 43 697.1 discloses a process which enables the production of formic acid formates on an industrial scale in a high space-time yield, with great flexibility in terms of composition and using readily accessible raw materials, and allows simple process design with low investment costs and low energy requirements.
• the process is based on methyl formate, hereinafter abbreviated as MeFo. Partial hydrolysis of MeFo produces a stream containing formic acid and the non-hydrolyzed portion MeFo is converted to the corresponding metal formate by saponification. Mixing the formic acid and the stream containing metal formate gives the formic acid formate.
• MeFo is an important intermediate in the production of formic acid and is obtained industrially by continuous carbonylation of methanol in the liquid phase in the presence of sodium or potassium methylate as a catalyst at temperatures in the range from about 50 to 150 ° C (see Ullmann's Encyclopedia of jjtidustrial Chemistry, 6 ft edition, 2000 electronic release, chapter "FORMIC ACID - Production”).
• the reaction is a homogeneously catalyzed equilibrium reaction in which the balance is shifted towards MeFo with increasing carbon monoxide partial pressure and falling temperature.
• the known methods are operated at a pressure of up to 30 MPa abs and a temperature of 50 to 150 ° C.
• alkali metal formate In the production of MeFo mentioned, two undesirable side reactions occur in particular, which can lead to serious problems in the continuously operated process. Both side reactions lead to the formation of alkali metal formate.
• the alkali metal methylate used reacts with any traces of water introduced in a hydrolysis reaction to form alkali metal formate and methanol.
• the alkali metal methylate used also reacts with existing MeFo to form alkali metal formate and dimethyl ether. Due to its insufficient solubility in the reaction medium, the alkali metal formate can then lead to deposits in the apparatus and pipelines or even blockage of pipes and valves.
• the risk of salt precipitation is particularly high with a high methanol conversion and thus a high concentration of MeFo and can therefore be reduced in principle by setting a partial conversion while ensuring a low concentration of MeFo.
• DE patent 926 785 describes a high-pressure process operating at 30 MPa, in which only a low catalyst concentration of 0.25% by weight sodium (corresponding to 0.59% by weight sodium methylate) is used to reduce the salt separation. In addition, the reactor contents are continuously stirred in order to keep the separated amounts of salt in suspension.
• the liquid reactor discharge, which contains about 90% MeFo, is expanded and worked up by distillation.
• DE-Auslegeschrift 1,046,602 describes a continuous, two-stage process in the presence of 0.5 to 5% by weight of alkali metal methylate at a pressure of 5 to 30 MPa. Deposits are to be prevented by ensuring a turbulent flow in the reactor. The total conversion of methanol is about 90%. The liquid reactor discharge is let down and worked up by distillation.
• WO 96/26178 describes a high-pressure process in which the reaction takes place in the presence of 0.05 to 0.2% by weight of alkali metal methylate at a pressure of 21 to 25 MPa.
• a good dispersion of the carbon monoxide, for example through a jet nozzle, enables a sufficiently high conversion to be achieved despite the low catalyst concentration.
• the concentration of MeFo in the reactor discharge is up to 97% by weight. The liquid reactor discharge is let down and worked up by distillation.
• DE-A 2 243 811 describes a process in which the reaction is carried out in the presence of 0.4 to 1.5% by weight of alkali metal methylate in countercurrent mode at a pressure of 4 to 30 MPa and which has a plurality of reaction zones connected in series.
• EP-A 0 617 003 describes a process in which the reaction is carried out in the presence of 0.4 to 1.5% by weight of alkali metal methylate at a pressure of 1 to 30 MPa. First, the reactants are brought together in a mixing zone and at least partially converted. The reaction solution obtained is finally saturated with carbon monoxide and fed to a post-reaction zone without the addition of further starting materials. The liquid reactor discharge is let down and worked up by distillation.
• WO 01/07392 describes a process in which the reaction takes place in the presence of 0.05 to 0.5% by weight of alkali metal methylate at a carbon monoxide pressure of 9 to 18 MPa.
• the liquid reactor discharge which contains about 60 to 95% by weight of MeFo, is fed to a distillation column to separate the MeFo.
• the remaining catalyst and methanol-containing bottom stream is recycled again, with residual catalyst and catalyst degradation products being withdrawn from a partial stream thereof via a desalination device.
• space-time yields in the range from 370 to 880 g / l-h MeFo were achieved.
• US 4,661,624 describes a two-stage process with recycling of the catalyst-containing, methanolic solution.
• the reaction is carried out at a pressure of 0.48 to 6.9 MPa (70 to 1000 psia) and a concentration of alkali metal methylate of 1 to 8 mol% (corresponding to 1.7 to 13.5% by weight of sodium methylate).
• further methanol is added in countercurrent mode in order to convert the remaining carbon monoxide.
• the process is operated at an extremely low conversion, so that the liquid reactor discharge contains only about 2 to 20 mol% of MeFo. It is fed to a distillation column to separate the MeFos. The remaining bottom stream containing catalyst and methanol is recycled.
• DE patent specification 863 046 describes a continuously operating low-pressure process in which methanol and 1 to 2% by weight of sodium (corresponding to 2.3 to 4.7% by weight of sodium methylate) in a bubble column equipped with packing elements from top to bottom and Carbon monoxide is fed in countercurrent from bottom to top and reacted at a pressure of about 2.5 to 3.0 MPa (25 to 30 atmospheres).
• the reaction mixture is continuously removed from the bottom of the reactor and carried out for working up by distillation.
• the gas withdrawn from the top of the reactor is passed through a cooler, freed of entrained MeFo in a separator and sent to
• DE-B 880 588 A method improved compared to DE 863 046 is described in DE-B 880 588.
• methanol and 1.6 to 2.5% by weight of sodium are fed with carbon monoxide in cocurrent from the bottom upwards in a bubble column equipped with packing elements and implemented at a pressure of up to 3.0 MPa (up to 30 atmospheres).
• Liquid reaction mixture is removed from a gas dome located at the reactor head and fed back to the reactor base via a circulation pump.
• the gaseous phase is removed, passed through a cooler, then freed from entrained MeFo in a separator and sent to Ensuring a sufficiently high gassing flow, mixed with fresh carbon monoxide, returned to the reactor.
• the entire MeFo is withdrawn via the gas phase and, after the condensation, fed to the working-up by distillation.
• DE-A 102 17 528.4 describes a process for the production of MeFo by reacting methanol with carbon monoxide at a pressure of 0.5 to 10 MPa absolute and a temperature of 50 to 150 ° C. in the presence of a metal alcoholate as catalyst in a reactor, in which a gas stream is withdrawn from the reactor, MeFo entrained in this gas stream is separated off by condensation and the remaining gas stream is returned to the reactor in whole or in part as a recycle gas stream, with at least one area of the reactor in which the gas essentially flows in one direction, sets an average empty gas pipe speed of 1 to 20 cm / s.
• This method is particularly advantageous with regard to the investment and energy costs, the consumption of catalyst and the space-time yield of MeFo, which is 100 g / 1 ⁇ h.
• the solution consists in a process for the production of formic acid formates, according to which
• the liquid stream I is mixed with the liquid stream II to obtain the corresponding formic acid formate, which is characterized in that the liquid stream I or a precursor thereof, the liquid stream LT or a precursor thereof or the mixture of the liquid streams I and II a liquid stream m containing the following components, each with a proportion of> 0.1% by weight:
• a metal methanolate must have been used as the catalyst for the carbonylation in order to prevent foreign substances from being introduced into the process for the production of formic acid formates via the coupling stream.
• liquid stream HI contains only substances that are already present in the process for producing formic acid formates.
• the coupling stream should not be the total stream of the reaction mixture from the MeFo production, but rather a stream that is concentrated in relation to the proportion of metal formate.
• the aforementioned separation of MeFo and methanol from the liquid stream IV can preferably be carried out by distillation in a column by direct introduction of water vapor.
• the liquid stream HI is obtained as a side stream from its reactor, in which MeFo is produced by carbonylation of methanol with carbon monoxide at a pressure of 0.5 to 10 MPa absolute and a temperature of 50 to 150 ° C., at which the reactor is turned on withdraws a gas stream from the upper region thereof, separates MeFo carried from the gas stream by condensation and returns the remaining gas stream to the reactor in whole or in part as a recycle gas stream, one in at least one area of the reactor in which the gas flows essentially in one direction average gas empty tube speed of at least 1 to 20 cm / s, preferably from at least 3 to 10 cm / s.
• the metal methoxide is preferably used as a homogeneous catalyst in the carbonylation of methanol with carbon monoxide in a concentration of 0.01 to 2 mol / kg of liquid reaction mixture, potassium methoxide being preferably chosen as the metal methoxide.
• the carbonylation of methanol to MeFo is preferably carried out at a pressure of 2 to 4 MPa absolute and a temperature of 60 to 85 ° C.
• a preferred molar ratio of the total amount of the methanol fed to the reactor and the amount of freshly fed carbon monoxide is set in the range from 1.4 to 3.3 to 1, preferably 2 to 1.
• a bubble column is used as the reactor for the production of MeFo and the same is operated in relation to the supply of the liquid stream containing methanol and the gas stream containing carbon monoxide in a cocurrent mode.
• the gas stream withdrawn from the reactor can be separated in a rectification column in a bottom stream containing MeFo and a top stream containing carbon monoxide and MeFo, MeFo entrained from the top stream can be separated off by condensation and the remaining gas stream can be returned to the reactor in whole or in part as a recycle gas stream.
• reaction mixture of the partial hydrolysis from process step (a) is separated by distillation into a lower-boiling stream V, comprising MeFo and methanol, and the lower-boiling stream I, comprising formic acid and water.
• the molar proportion of formic acid based on the formate anion y is generally from 0.01 to 100, preferably from 0.05 to 20, particularly preferably from 0.5 to 5 and in particular from 0.9 to 3.1.
• inorganic or organic cation M x + is in principle irrelevant, provided that it is stable under the conditions under which the formic acid formate is to be handled. This includes, for example, the stability towards the reducing formate anion.
• Possible inorganic cations are the mono- and / or polyvalent metal cations of the metals from group 1 to 14 of the periodic table, such as lithium (Li + ), sodium (Na + ), potassium (K + ), cesium (Cs + ), Magnesium (Mg 2+ ), calcium (Ca 2+ ), strontium (Sr 2 " * " ) and barium (Ba 2+ ), preferably sodium (Na + ), potassium (K + ), cesium (Cs + ) and calcium (Ca 2+ ) called.
• Possible organic cations are unsubstituted ammonium (NIL *) and ammonium substituted by one or more carbon-containing radicals, which can optionally also be linked to one another, such as methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, pyrrolidinium, N-methylpyrrolidinium , Called piperidinium, N-methylpiperidinium or pyridinium.
• NIL * unsubstituted ammonium
• carbon-containing radicals which can optionally also be linked to one another, such as methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, pyrrolidinium, N-methylpyrrolidinium , Called piperidinium, N-methylpiperidinium or pyridinium.
• a carbon-containing organic radical is to be understood as an unsubstituted or substituted, aliphatic, aromatic or araliphatic radical with 1 to 30 carbon atoms.
• the carbon-containing organic radical can be a monovalent or also polyvalent, for example di- or trivalent, radical.
• MeFo is partially hydrolyzed with water to formic acid and methanol. Partial is to be understood to mean that only a part of the MeFos supplied is hydrolyzed.
• process step (a) the known processes for the hydrolysis of MeFo can be used.
• Other suitable hydrolysis processes are also described, for example, in EP-A 0 005 998 and EP-A 0017 866.
• the hydrolysis is generally carried out at a temperature of 80 to 150 ° C. and a pressure of 0.5 to 2.0 MPa abs.
• reaction apparatuses which are suitable for reactions in the liquid phase can be used as reaction apparatuses. Examples include stirred kettles and jet loop reactors. The use of a cascaded reactor is preferred.
• the formic acid formed or additional catalysts can be used as acid catalysts.
• the additional catalysts can be homogeneous or heterogeneous in nature.
• heterogeneous catalysts are acid ion exchangers, such as polysulphonic or poly (perfluoroalkylene) sulfonic acids (for example Nafion ® by DuPont), and as examples of homogeneous catalysts strong inorganic or organic acids, such as sulfuric acid, hydrochloric acid or alkyl and tolylsulfonic acids mentioned. If homogeneous catalysts are used, they must generally be separated off in a subsequent step.
• the acidic catalysts are usually found in the form of their salts in the formic acid formate.
• the partial hydrolysis is particularly preferably carried out in the presence of formic acid as an acid catalyst, as a result of which the addition of an additional catalyst and its subsequent separation or the possible contamination of the formic acid formates is eliminated.
• a formic acid concentration of about 0.1 to 2% by weight, based on the liquid mixture comprising water and MeFo, is introduced at the reactor inlet by a targeted addition of formic acid or a stream containing formic acid.
• the reaction mixture obtained from the partial hydrolysis thus contains unreacted MeFo, formic acid, methanol and, owing to the preferred use of an excess of water, water.
• the aqueous reaction mixture preferably contains 5 to 15 mol%, particularly preferably 8 to 12 mol% of formic acid, 3 to 30 mol%, particularly preferably 6 to 12 mol% MeFo and 6 to 15 mol%, particularly preferably 8 to 12 mol% methanol.
• MeFo and methanol are separated off from the reaction mixture obtained in process stage (a) by distillation to form the stream containing formic acid and water.
• MeFo and methanol can be separated off together in the form of a stream or separately in the form of a stream containing MeFo and a stream containing methanol.
• MeFo and methanol are separated or removed together in the upper part of the column.
• the stream I containing formic acid and water is generally taken from the bottom.
• Preferred in process step (b) is the joint separation of a stream containing MeFo and methanol.
• the design and operation of the distillation column are primarily dependent on the composition of the stream supplied and the desired purities of the two product streams and can be determined in a known manner by a person skilled in the art.
• the MeFo and methanol-containing, lower-boiling, liquid stream V can preferably be returned to process stage (a). Provision of the liquid stream II
• the liquid stream ⁇ containing a metal formate, can be obtained by saponification by passing the stream V comprising MeFo and methanol in process stage c)
• the basic compound to be used preferably has a pK a value of the corresponding acid of the corresponding dissociation level of> 3.5, particularly preferably of> 9 and very particularly preferably of> 10, measured at 25 ° C. in aqueous solution.
• the basic compound can be inorganic or organic in nature.
• the basic compound can be a salt or a covalent compound.
• the corresponding acid of the corresponding dissociation level is to be understood as the acid formed by the formal addition of a proton (H + ).
• M and x have the meaning given under (I) and A corresponds to an inorganic or organic anion with the charge "a-”.
• the corresponding acid of the corresponding dissociation level thus corresponds to HA (a_1) " .
• the corresponding dissociation equation which is relevant for the pK a value to be used , is
• Suitable basic compounds are the salts M x + a A a " x (H), in which M x + stands for a mono- or polyvalent metal cation of a metal as described above and A a" for an anion as listed in Table la and the covalent compounds B as listed in Table 1b.
• Table la Possible anions A a "of suitable basic compounds and pK a values (measured at 25 ° C. in aqueous solution) of the corresponding acids of the corresponding dissociation stages.
• Table 1b Possible covalent bases B as suitable basic compounds and pKa values (measured at 25 ° C. in aqueous solution) of the corresponding acids of the corresponding dissociation stages.
• the basic compounds used are preferably lithium hydroxide, lithium hydrogen carbonate, lithium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium hydroxide, potassium hydrogen carbonate, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate and / or ammonia, particularly preferably sodium hydroxide, sodium hydrogen carbonate, sodium carbonate,
• Potassium hydroxide, potassium hydrogen carbonate, potassium carbonate and / or ammonia and particularly preferably sodium hydroxide, sodium carbonate, potassium hydroxide and / or potassium carbonate, in particular sodium hydroxide and / or potassium hydroxide.
• the type of addition of the basic compounds is generally immaterial. They can be added in solid, liquid or gaseous form, as a pure substance, as a mixture of substances or as a solution. Examples include the addition in the form of water Solutions (e.g. aqueous solutions of alkali salts or ammonia water), in the form of solid compounds (e.g. powders of alkali salts), are called in the gaseous state (e.g. gaseous ammonia). The addition in the form of their aqueous solutions is preferred.
• water Solutions e.g. aqueous solutions of alkali salts or ammonia water
• solid compounds e.g. powders of alkali salts
• gaseous state e.g. gaseous ammonia
• the order in which the starting materials are added is generally also immaterial.
• the basic compound in solid or liquid form (e.g. as an aqueous solution) and then to enter the stream containing MeFo in liquid or gaseous form.
• the MeFo-containing stream in liquid form and then to add the basic compound.
• the molar ratio of the MeFo to the basic compound is advantageously stoichiometric, that is to say in such a way that the MeFo added reacts with the basic compound added to the corresponding formate and water in accordance with the reaction stoichiometry.
• the decisive factor for this is the so-called molar equivalent of the basic compound, taking into account all dissociation steps which lead to the addition of protons to corresponding acids which have a pK a value of> 3, measured at 25 ° C in aqueous solution are.
• potassium hydroxide a MeFo / potassium hydroxide molar ratio of 1.0 should preferably be chosen, since this corresponds to the formation of potassium formate:
• the amount of water to be used in process step (c) can vary over a wide range. In general, 20 to 90% by weight and preferably 40 to 50% by weight of water, based on the amount of MeFo supplied, is used in the reaction. In general, the water is added via an aqueous solution of the basic compound, although the addition of pure water is also possible.
• the reaction of the MeFo-containing stream in process step (c) with the basic compound mentioned in the presence of water is generally carried out at a temperature from 0 to 150 ° C., preferably from 30 to 120 ° C. and particularly preferably from 50 to 80 ° C. by.
• the pressure is generally 0.05 to 1 MPa abs, preferably 0.08 to 0.5 MPa abs and particularly preferably 0.09 to 0.15 MPa abs.
• the reaction of the MeFo-containing stream in process step (c) with the basic compound mentioned in the presence of water is in principle independent of the removal of the methanol by distillation.
• the methanol can be removed by distillation before, together with or after the reaction mentioned. Preference is given to removing the methanol by distillation together with or after the reaction mentioned.
• reaction apparatuses which are suitable for reactions in the liquid phase can in principle be used for the reaction. Examples include stirred tanks and jet loop reactors.
• the methanol is then separated off by distillation in a separate step, usually in a distillation column.
• process step (ii) it is particularly preferred to carry out the removal of the methanol by distillation (process step (ii)) together with the Reaction of the MeFos with the water and the basic compound with conversion into the formate and water-containing stream U (process stage (i)) in a column.
• the MeFo and methanol-containing stream from process stage (b) is advantageously added below the addition point of the water and the basic compound. Since the MeFo and the methanol rise in the column and the water and the basic compound flow downwards, the column has a range which is suitable for the reaction mentioned. The methanol rises and can be isolated overhead. Since the production of MeFo is generally carried out by carbonylation of methanol, it is particularly advantageous to recycle the methanol isolated over the top as a feedstock for the production of MeFo, the methanol to be recycled in this variant also being able to contain residual amounts of MeFo. It is therefore only necessary in the overall balance to replace the low methanol losses with fresh methanol.
• the stream containing the aqueous formate flows downward in the column and is taken off as the bottom stream. It may be advantageous to take part of the water as a side stream at the lower end of the column and to return it to the hydrolysis. This measure enables a more concentrated aqueous solution of the corresponding formate to be obtained.
• the required residence time in the saponification section of the column can be provided, for example, by suitable internals, such as Thormann trays, or, if appropriate, by an external reaction volume.
• suitable internals such as Thormann trays
• an external reaction volume When an external reaction volume is provided, the stream to be saponified is removed from the column at a suitable point by a side draw, fed to the external reaction apparatus and fed back to the column at a suitable point. Both variants are primarily considered to be equivalent.
• the column is designed in the manner customary and known to those skilled in the art.
• the carbonylation mentioned proves to be particularly advantageous, since it enables the use of readily and easily accessible starting materials and is technically simple to carry out.
• A.F. Hollemann, N. Wiberg, Textbook of inorganic chemistry, Walter de Gruyter Verlag Berlin New York, 1985, 91st - 100th edition page 722
• Sodium formate by introducing carbon monoxide into sodium hydroxide solution at 150 to 170 ° C and a pressure of 3 to 4 bar and, according to page 947 of the same textbook, produce potassium formate by the action of carbon monoxide on an aqueous solution of potassium sulfate and quicklime at 230 ° C and 30 bar.
• sodium formate can be used, for example, by the action of carbon monoxide on aqueous sodium hydroxide solution at 180 ° C and 1.5 to 1.8 MPa of a reaction tower can be won.
• the aqueous sodium hydroxide solution trickles from top to bottom, whereas the carbon monoxide flows in countercurrent from bottom to top.
• the provided streams I, containing formic acid and U, containing a metal formate are mixed.
• liquid stream I and the liquid stream LT are added is generally immaterial.
• the specific process conditions, in particular with regard to temperature and pressure, and the specific apparatus used for mixing the liquid streams I and LT are in principle not subject to any restrictions and can be determined in a suitable manner by a person skilled in the art. Further details on this are contained in DE-A 102 37 379 cited above.
• the liquid stream I and the liquid stream LT are preferably mixed in a column, the formic acid formate and water-containing bottoms liquid are withdrawn therefrom and separated from the bottom liquid formic acid formate by crystallization, spray granulation, spray drying or melt crystallization and the separated formic acid formate is isolated.
• the invention also relates to the use of the formic acid formates produced by utilizing a coupling current from the MeFo process for the preservation and / or acidification of plant and animal substances.
• the invention furthermore relates to the use of the formic acid formates produced according to the invention for the preservation and / or acidification of plant and animal substances.
• examples include the use of formic acid formates for the preservation and acidification of grass, agricultural plants, fish and fish and meat products, as described, for example, in WO 97/05783, WO 99/12435, WO 00/08929 and WO 01/19207 ,
• the invention furthermore relates to the use of the formic acid formates produced according to the invention for the treatment of bio-waste.
• the use of formic acid formates for the treatment of biowaste is described, for example, in WO 98/20911.
• the invention furthermore relates to the use of the formic acid formates produced according to the invention as an additive in animal nutrition and / or as a growth promoter for animals, such as for breeding sows, fattening pigs, poultry, calves, cows and fish.
• a growth promoter for animals such as for breeding sows, fattening pigs, poultry, calves, cows and fish.
• the use mentioned is described for example in WO 96/35337.
• Preference is given to using the formic acid potassium formates prepared in accordance with the invention, in particular potassium formate, as an additive in animal nutrition and / or as growth promoters for animals, especially for breeding sows and fattening pigs.
• compositions may be mentioned as particularly preferred mixtures for the preferred use of the formic acid potassium formates produced by the process according to the invention as an additive in animal nutrition and / or as growth promoter for animals.
• the use of the potassium diformiate produced according to the invention is very particularly preferred as an additive in animal nutrition and / or as a growth promoter for animals in the form of a product having the composition 98.0 ⁇ 1% by weight potassium diformate, 1.5 ⁇ 1% by weight silicate and 0.5 ⁇ 0.3 wt% water.
• Figure 2 shows a simplified process of the flow diagram of a particularly preferred
• Embodiment in which the metal formate is made by carbonylation is made by carbonylation.
• the simplified process flow diagram of which is shown in FIG. 1 MeFo and water returned from the process and containing formic acid are added to the cascaded hydrolysis reactor A via line 1.
• the two starting materials are premixed (as shown in the flow diagram) or brought separately to the desired inlet temperature in a heat exchanger.
• reaction mixture originating from the hydrolysis stage (process stage (a)), which contains unreacted MeFo, water, formic acid and methanol, is fed via line 2 to column B, in which a distillative separation of the reaction mixture into a top stream containing MeFo and methanol and an aqueous formic acid-containing bottoms stream is carried out (process stage (b)).
• a liquid form TU containing metal formate, metal methoxide, methanol and MeFo is fed to line 2 from a process for the production of MeFo by carbonylation of methanol.
• the overhead stream V containing MeFo and methanol is fed to column C via line 3.
• the aqueous basic compound particularly preferably potassium hydroxide solution
• the aqueous basic compound is fed to column C above the feed point of the MeFo and methanol-containing stream via line 5.
• a liquid stream HI from the production of MeFo is fed to the column C, preferably approximately in the middle region thereof.
• Methanol is recovered at the top of column C and preferably recycled to carbon dioxide for the production of MeFo again.
• part of the water is removed and returned to the hydrolysis stage via line 6.
• An aqueous potassium formate solution is obtained as the bottom product.
• the stream I from process stage (b) containing the aqueous formic acid is fed to column E via line 7.
• the stream LT containing the aqueous formate solution from process stage (c) is fed in via line 8.
• Column E is advantageously operated in such a way that a concentrated mixture containing formic acid, formate and water and having a water content of generally 10 to 40% by weight is obtained as the bottom product.
• a portion of the water is taken from column E in the form of a water stream containing formic acid as the top product and is returned via line 13 to the hydrolysis stage.
• Part of the small amount of water stream containing formic acid can optionally be removed from the system via line 12.
• the bottom product of column E is fed via line 9 to an apparatus G suitable for crystallization, for example a so-called cooling disk crystallizer. The crystallization takes place primarily by lowering the temperature.
• the crystals obtained are fed to the apparatus F together with the supernatant solution for separation.
• the separation is preferably carried out by Centrifugation.
• the separated crystals are removed via line 10 and can be dried and / or assembled, for example, in optional subsequent stages.
• the mother liquor obtained is returned to column E via line 11.
• Column E is advantageously operated in such a way that a concentrated mixture containing formic acid, metal formate and water and having a water content of generally 0.5 to 30% by weight is obtained as the bottom product.
• a portion of the water supplied is removed from column E in the form of a water stream containing formic acid as the top product and returned via line 19 to the hydrolysis stage.
• Part of the small amount of water stream containing formic acid can optionally be removed from the system via line 18.
• the bottom product of column E is fed via line 15 to an apparatus G suitable for spray granulation, spray drying or melt crystallization.
• the solid formic acid formate obtained is removed via line 16 and can be further dried and / or packaged, for example, in optional subsequent stages.
• the condensate obtained can optionally be returned to column E via line 17 or discharged from the system.

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• 2003
  • 2003-05-14 DE DE10321733A patent/DE10321733A1/de not_active Withdrawn
• 2004
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  • 2004-05-14 CN CNA2004800129093A patent/CN1787987A/zh active Pending
  • 2004-05-14 RU RU2005138727/04A patent/RU2005138727A/ru not_active Application Discontinuation
  • 2004-05-14 KR KR1020057021457A patent/KR20060013536A/ko not_active Application Discontinuation
  • 2004-05-14 CA CA002526912A patent/CA2526912A1/en not_active Abandoned
  • 2004-05-14 AR ARP040101638A patent/AR044327A1/es unknown
  • 2004-05-14 MX MXPA05011691A patent/MXPA05011691A/es unknown
  • 2004-05-14 BR BRPI0409827-7A patent/BRPI0409827A/pt not_active IP Right Cessation
• 2005
  • 2005-11-03 NO NO20055153A patent/NO20055153L/no not_active Application Discontinuation

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