Method of improving the crushing strength and reducing the dust formation and the caking tendency of urea, and urea composition
EP 1761484 A1 (text from WO2006004412A1)
EP 1761484 A1 (text from WO2006004412A1)
Abstract
The invention relates to a method of improving the crushing strength and reducing the dust formation and the caking tendency of urea particles by the addition of an organic compound to the molten urea, where at least one carbohydrate and optionally a polyvinyl compound is added to the urea. The invention also relates to a composition to be used as a urea additive.
Claims (OCR text may contain errors)
Claims
1. A method of improving the crushing strength and reducing the dust formation and the caking tendency of urea particles by the addition of an additive to the molten urea, characterized in that at least one carbohydrate and optionally a polyvinyl compound is added to the urea.
2. A method according to claim 1 , characterized in that the carbohydrate added is selected among monosaccharide, disaccharide, oligosaccharide, polysaccharide or a mixture thereof.
3. A method according to anyone of the claims 1 to 2, characterized in that at most 5 wt % carbohydrate, based on the amount of urea, is added.
4. A method according to anyone of the claims 1 to 3, characterized in that 0.02 - 2 wt % carbohydrate, based on the amount of urea, is added.
5. A method according to anyone of the claims 1 to 4, characte rized in that a polyvinyl compound of the general formula (CHX-CHY)n, where n = 4 - 10000, and X and Y independently of one another are selected from the group consisting of a hydrogen atom and a polar organic group, is added. 6. A method according to anyone of the claims 1 to 5, characterized in that a compound of the formula specified in claim 5 is added, wherein the said polar organic group is selected from a carboxylic acid group, an ester group, a hydroxyl group, an amine group or an amide group.
7. A method according to anyone of the claims 1 to 6, characterized in that a polyvinyl compound is added as described in claim 5 or 6, wherein X is a hydrogen atom and Y substantially consists of a hydroxyl group.
8. A method according to anyone of the claims 1 to 7, characterized in that at least 70 %, preferably at least 80 %, of Y consists of a hydroxyl group.
9. A method according to anyone of the claims 1 to 8, characterized in that an aqueous solution of the polyvinyl compound having a concentration of from 0.01 to 1 wt %, based on the amount of urea, is added.
10. A method according to anyone of the claims 1 to 9, characterized in that an aqueous solution of the polyvinyl compound having a concentration of from 0.05 to 0.5 wt %, based on the amount of urea, is added.
11. A method according to anyone of the claims 1 to 10, characterized in that the carbohydrate is added to the urea as a solid, or is dissolved in a solvent or an aqueous solution of the polyvinyl compound or a urea solution before being added to the urea. 12. Composition to be used in the method according to anyone of the preceding claims as a urea additive.
Description (OCR text may contain errors)
Method of improving the crushing strength and reducing the dust formation and the caking tendency of urea, and urea composition.
The invention relates to a method of improving the crushing strength and reducing the dust formation and the caking tendency of urea particles by the addition of an organic compound to the urea.
It is generally known that urea particles are subject to crushing during production, storage and transport. Up to 25 wt % of the urea particles may be crushed if the urea fertilizer is moved into a storage bin or storage ship at a relatively high temperature of e.g. more than 40 0C. Even though the urea particles as such hardly absorb any moisture and are virtually non- susceptible to caking, high percentages of crushed particles do lead to dust problems with a strong caking tendency.
It is also known that a number of chemical compositions can be used as additives to improve the crushing strength, the caking tendency and the resistance to moisture. Formaldehyde, hexamethylenetetramine and formaldehyde/ urea condensate products are applied as crushing strength improvers, while the combination polyvinyl acetate)/surfactant (US 4,812,158) is used to reduce the caking tendency.
International application WO 00/66515 describes a conditioned fertilizer product comprising urea containing fertilizer and a conditioning amount of lactic acid derived conditioning agent. The conditioning agent is preferably included at a concentration of between about 0.1 % by weight and about 5 % by weight. The conditioning agent is preferably lactic acid, lactide and/or polylactide. A method for conditioning fertilizer is provided including a step of mixing urea-containing fertilizer and conditioning agent at a temperature of between about 1350C and about 145 0C. All these additives must either be added in relatively large quantities, or the toxic characteristics make them difficult to handle. Moreover, the use of a surface active component as in polyvinyl acetate)/surfactant, results in increased foaming when the urea is used for industrial applications, such as resin production, whilst formaldehyde derivatives are unsuitable in the case of melamine production. There is also a major difference with respect to the use of additives. Both formaldehyde derivatives and the compositions according to the invention are admixed to a urea melt. The combination polyvinyl acetate)/surfactant is, however, sprayed onto a preformed particle.
GB-A-1217106 describes a method of reducing the caking of urea by using a polyvinyl alcohol) having a high molecular weight as an anticaking additive. More in particular, according to this method, an aqueous solution of the additive is admixed to an aqueous solution of urea. Preferentially, an amount of additive of from 0.005 to 5 wt %, based on the weight of the urea, is admixed. The concentration of the aqueous urea solution is initially 80%, according to the example given; after admixture of the solution of the additive, concentration up to 95% takes place at elevated temperature, after which the urea is allowed to crystallize by cooling.
International application WO 02/20471 discloses a method in which a combination of a polyvinyl compound and inorganic salts is admixed with a urea melt. Both the crushing strength and the impact resistance of the resulting granulate appeared to be improved compared to untreated urea. In addition, the compressibility of the urea was found to be decreased substantially. The latter observation can be a great advantage as the urea granulates will be less prone to deformation upon storage. However, the introduction of inorganic salts, such as aluminium sulphate, in urea results in a strong decrease of the pH upon dissolving the urea in water. This can be a serious disadvantage when using urea for technical applications, such as the production of resins. International application PCT/EP03/11070 relates to a method for improving the crushing strength, impact resistance and the compressibility of urea granules by the addition of a compound to the molten urea, where said compound comprises both a polyvinyl compound and an organic molecule consisting of 1 - 10 carbon atoms and 1 - 10 polar organic groups. The polyvinyl compound is preferably combined with pentaerythritol. In some aspects, it would be of interest to find other urea additives as alternatives to already known additives, particularly additives that would reduce the caking tendency of urea particles.
It was therefore an object of the invention to provide a method by means of which urea having an improved crushing strength as well as a reduced dust formation and a low caking tendency is obtained and by means of which the abovementioned drawbacks are overcome.
It was also an object to find alternative additives to already existing urea additives.
It was a further object that the additives should have a low toxicity.
It has been found that the addition of a composition comprising an organic molecule of the carbohydrate type such as monosaccharide, disaccharide, oligosaccharide, polysaccharide or a mixture thereof, to the urea melt leads to an improvement of both the hardness and the caking tendency of the urea particles formed.
In another embodiment, a composition comprising both a carbohydrate and a polyvinyl compound gives a similar improvement. The organic components can be added either separately to the molten urea or together with the aqueous solution of the polyvinyl compound. According to a preferred embodiment, the total added amount of carbohydrates is at most 5 % by weight based on the total amount of urea. The present application relates to an intimate mixture of urea, at least one carbohydrate and optionally a polyvinyl compound, resulting in increased hardness of the composition compared to untreated urea. Preferably the polyvinyl compound is a polyvinyl alcohol), whereas the carbohydrate can be a mono-, di-, oligo or a polysaccharide or a mixture thereof. Preferred carbohydrates are dextrose, fructose, sucrose, maize starch, potato starch, lactose, maltose, guar and xanthan gum.
The present invention will in its widest scope comprise a method of improving the crushing strength and reducing the dust formation and caking tendency of urea particles by the addition of an organic compound to the molten urea, where at least one carbohydrate and optionally a polyvinyl compound is added to the urea. The added carbohydrate is monosaccharide, disaccharide, oligosaccharide, polysaccharide or a mixture thereof. At most 5 wt % carbohydrate, based on the amount of urea, is added. Preferably, 0.02 - 2 wt % carbohydrate, based on the amount of urea, is added. A polyvinyl compound of the general formula (CHX - CHY)n, where n = 4 - 10 000, and X and Y independently of one another are selected from the group consisting of a hydrogen atom and a polar organic group, is added. The polar organic group is preferably selected from a carboxylic acid group, an ester group, a hydroxyl group, an amine group or an amide group. X is preferably a hydrogen atom and Y preferably substantially consists of a hydroxyl group. At least 70 %, preferably at least 80 %, of Y consists of a hydroxyl group. An aqueous solution of the polyvinyl compound having a concentration of from 0.01 to1 wt %, based on the amount of urea, is added. Preferably, an aqueous solution of the polyvinyl compound having a concentration of from 0.05 to 0.5 wt %, based on the amount of urea, is used. The carbohydrate might be added to the urea as a solid, or dissolved in a solvent or an aqueous solution of the polyvinyl compound or a urea solution before being added to the urea. The invention also relates to a composition to be used in the method as described above, as a urea additive.
The invention is further described and explained in the following experiments.
To demonstrate the effect of the invention, a number of experiments were carried out, employing methods that are representative for production and for testing the quality of the urea particles produced.
Urea particles were produced by admixing the additive, being in the form of a solid, a viscous liquid or an aqueous solution (having the concentrations indicated in the experiments), with a urea melt consisting of more than 96 w/w % urea and less than 4 w/w % water. Thereafter the urea melt was particulated in a granulation process. The particles were collected and kept in an airtight bottle until the analyses were performed.
The crushing strength was determined by subjecting individual particles of urea of 3.15 mm to a measured force, applied by means of a metal plunger. The force, at which the particle fractures, was taken as a measure of strength. The average strength of 20 particles were reported.
The caking index was measured by the following procedure: An amount of particles was pressurized at 143 kgf (2 bar applied on a surface of 69.96 cm2) for 24 hrs at 270C. The lump of material was then taken out and broken, the amount of force (kgf) needed for this is taken as a measure for the caking tendency.
Dust formation in the products was measured by the following procedure: Clean air was blown through a glass spouted bed (85 mm in diameter) filled with 400 g of urea particles for 2 minutes at a flow rate of 25 Nm3/h. The dust formation is the weight loss of the product after the air treatment in the spouted bed.
Based on experience, the crushing strength should be > 3 kgf , the caking tendency should be < 75, and the dust formation should be < ~ 500 mg/kg.
Experiment 1
Different carbohydrates were added to the urea melt, and particulated as described above. The addition of carbohydrates was compared with urea without additive and with a standard product with urea-formaldehyde conditioning agent, UF80 (from Dynea, a mixture of urea/formaldehyde/water in a ratio of 23/57/20).
Table 1 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with different carbohydrates.
Table 1
![Figure imgf000007_0001]()
This experiment shows that both the hardness and caking tendency improved upon addition of the carbohydrates. The quality can be as good as or even better than a product treated with formaldehyde, especially with respect to the dust formation.
Experiment 2
5 An aqueous polyvinyl alcohol) solution (12 % PVA with a degree of hydrolysis > 80 %) was obtained from Holland Novochem in the Netherlands. The carbohydrate was mixed into the aqueous polyvinyl alcohol) solution and the resulting aqueous solution of carbohydrate and polyvinyl alcohol) was added to the urea melt, where after the melt was particulated. The 0 added carbohydrates were fructose and HFS42, which is a commonly available syrup comprising 71 wt % dry matter and 29 wt % water, where the dry matter comprises 42 wt % fructose, 53 wt % dextrose, 2.5 wt % maltose, 1 wt % malotriose, and 1.5 wt % polysaccharides. The combinations of carbohydrate and polyvinyl alcohol) were compared with urea without 5 additive and the standard product with urea-formaldehyde conditioning agent, UF80.
Table 2 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with o different combinations of carbohydrate and polyvinyl alcohol).
Table 2
![Figure imgf000008_0001]()
This experiment demonstrates that the addition of a combination of polyvinyl alcohol) and carbohydrate to a urea melt results in urea particles with improved crushing strength, low caking tendency and low dust formation. Experiment 3
An aqueous polyvinyl alcohol) solution (12 % PVA with a degree of hydrolysis > 80 %) was obtained from Holland Novochem in the Netherlands. The carbohydrate was mixed into the aqueous polyvinyl alcohol) solution and the resulting aqueous solution of carbohydrate and polyvinyl alcohol) was added to the urea melt, where after the melt was particulated. The added carbohydrates were fructose and HFS42. The combinations of carbohydrate and polyvinyl alcohol) were compared with urea without additive and with the standard product with urea-formaldehyde, UF80. In this experiment, the concentration of the urea melt was more than 99 w/w % urea and less than 1 w/w % water.
Table 3 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with different combinations of carbohydrates and polyvinyl alcohol).
Table 3
![Figure imgf000009_0001]()
This experiment demonstrates that the addition of a combination of polyvinyl alcohol) and carbonate to a urea melt results in urea particles with improved crushing strength, low dust formation and caking tendency, when an almost pure urea melt is used for pandiculation. The present invention shows that it is possible to improve the crushing strength, reduce the dust formation and the caking tendency of urea particles by the addition of at least one carbohydrate, with or without a polyvinyl compound, to the urea melt before pandiculation. The urea melt obtained by the method according to the present invention can be particulated by all common pandiculation methods. For certain pandiculation methods, for instance in fluid bed granulation processes, it could be possible to have a higher granulation temperature compared to granulation of urea without additive or with commonly used additives.
The additives according to the present invention can easily be added to the urea melt and do not require a preformed particle. The carbohydrates might be added to the urea melt as solids, they might be dissolved in a solvent or an aqueous solution of the polyvinyl compound or a urea solution before being added to the urea melt. The required amounts of the additives according to the present invention are lower than most other conditioning agents, and the toxicity is much lower than for the commonly used conditioning agent, formaldehyde.
The invention relates to a method of improving the crushing strength and reducing the dust formation and the caking tendency of urea particles by the addition of an organic compound to the urea.
It is generally known that urea particles are subject to crushing during production, storage and transport. Up to 25 wt % of the urea particles may be crushed if the urea fertilizer is moved into a storage bin or storage ship at a relatively high temperature of e.g. more than 40 0C. Even though the urea particles as such hardly absorb any moisture and are virtually non- susceptible to caking, high percentages of crushed particles do lead to dust problems with a strong caking tendency.
It is also known that a number of chemical compositions can be used as additives to improve the crushing strength, the caking tendency and the resistance to moisture. Formaldehyde, hexamethylenetetramine and formaldehyde/ urea condensate products are applied as crushing strength improvers, while the combination polyvinyl acetate)/surfactant (US 4,812,158) is used to reduce the caking tendency.
International application WO 00/66515 describes a conditioned fertilizer product comprising urea containing fertilizer and a conditioning amount of lactic acid derived conditioning agent. The conditioning agent is preferably included at a concentration of between about 0.1 % by weight and about 5 % by weight. The conditioning agent is preferably lactic acid, lactide and/or polylactide. A method for conditioning fertilizer is provided including a step of mixing urea-containing fertilizer and conditioning agent at a temperature of between about 1350C and about 145 0C. All these additives must either be added in relatively large quantities, or the toxic characteristics make them difficult to handle. Moreover, the use of a surface active component as in polyvinyl acetate)/surfactant, results in increased foaming when the urea is used for industrial applications, such as resin production, whilst formaldehyde derivatives are unsuitable in the case of melamine production. There is also a major difference with respect to the use of additives. Both formaldehyde derivatives and the compositions according to the invention are admixed to a urea melt. The combination polyvinyl acetate)/surfactant is, however, sprayed onto a preformed particle.
GB-A-1217106 describes a method of reducing the caking of urea by using a polyvinyl alcohol) having a high molecular weight as an anticaking additive. More in particular, according to this method, an aqueous solution of the additive is admixed to an aqueous solution of urea. Preferentially, an amount of additive of from 0.005 to 5 wt %, based on the weight of the urea, is admixed. The concentration of the aqueous urea solution is initially 80%, according to the example given; after admixture of the solution of the additive, concentration up to 95% takes place at elevated temperature, after which the urea is allowed to crystallize by cooling.
International application WO 02/20471 discloses a method in which a combination of a polyvinyl compound and inorganic salts is admixed with a urea melt. Both the crushing strength and the impact resistance of the resulting granulate appeared to be improved compared to untreated urea. In addition, the compressibility of the urea was found to be decreased substantially. The latter observation can be a great advantage as the urea granulates will be less prone to deformation upon storage. However, the introduction of inorganic salts, such as aluminium sulphate, in urea results in a strong decrease of the pH upon dissolving the urea in water. This can be a serious disadvantage when using urea for technical applications, such as the production of resins. International application PCT/EP03/11070 relates to a method for improving the crushing strength, impact resistance and the compressibility of urea granules by the addition of a compound to the molten urea, where said compound comprises both a polyvinyl compound and an organic molecule consisting of 1 - 10 carbon atoms and 1 - 10 polar organic groups. The polyvinyl compound is preferably combined with pentaerythritol. In some aspects, it would be of interest to find other urea additives as alternatives to already known additives, particularly additives that would reduce the caking tendency of urea particles.
It was therefore an object of the invention to provide a method by means of which urea having an improved crushing strength as well as a reduced dust formation and a low caking tendency is obtained and by means of which the abovementioned drawbacks are overcome.
It was also an object to find alternative additives to already existing urea additives.
It was a further object that the additives should have a low toxicity.
It has been found that the addition of a composition comprising an organic molecule of the carbohydrate type such as monosaccharide, disaccharide, oligosaccharide, polysaccharide or a mixture thereof, to the urea melt leads to an improvement of both the hardness and the caking tendency of the urea particles formed.
In another embodiment, a composition comprising both a carbohydrate and a polyvinyl compound gives a similar improvement. The organic components can be added either separately to the molten urea or together with the aqueous solution of the polyvinyl compound. According to a preferred embodiment, the total added amount of carbohydrates is at most 5 % by weight based on the total amount of urea. The present application relates to an intimate mixture of urea, at least one carbohydrate and optionally a polyvinyl compound, resulting in increased hardness of the composition compared to untreated urea. Preferably the polyvinyl compound is a polyvinyl alcohol), whereas the carbohydrate can be a mono-, di-, oligo or a polysaccharide or a mixture thereof. Preferred carbohydrates are dextrose, fructose, sucrose, maize starch, potato starch, lactose, maltose, guar and xanthan gum.
The present invention will in its widest scope comprise a method of improving the crushing strength and reducing the dust formation and caking tendency of urea particles by the addition of an organic compound to the molten urea, where at least one carbohydrate and optionally a polyvinyl compound is added to the urea. The added carbohydrate is monosaccharide, disaccharide, oligosaccharide, polysaccharide or a mixture thereof. At most 5 wt % carbohydrate, based on the amount of urea, is added. Preferably, 0.02 - 2 wt % carbohydrate, based on the amount of urea, is added. A polyvinyl compound of the general formula (CHX - CHY)n, where n = 4 - 10 000, and X and Y independently of one another are selected from the group consisting of a hydrogen atom and a polar organic group, is added. The polar organic group is preferably selected from a carboxylic acid group, an ester group, a hydroxyl group, an amine group or an amide group. X is preferably a hydrogen atom and Y preferably substantially consists of a hydroxyl group. At least 70 %, preferably at least 80 %, of Y consists of a hydroxyl group. An aqueous solution of the polyvinyl compound having a concentration of from 0.01 to1 wt %, based on the amount of urea, is added. Preferably, an aqueous solution of the polyvinyl compound having a concentration of from 0.05 to 0.5 wt %, based on the amount of urea, is used. The carbohydrate might be added to the urea as a solid, or dissolved in a solvent or an aqueous solution of the polyvinyl compound or a urea solution before being added to the urea. The invention also relates to a composition to be used in the method as described above, as a urea additive.
The invention is further described and explained in the following experiments.
To demonstrate the effect of the invention, a number of experiments were carried out, employing methods that are representative for production and for testing the quality of the urea particles produced.
Urea particles were produced by admixing the additive, being in the form of a solid, a viscous liquid or an aqueous solution (having the concentrations indicated in the experiments), with a urea melt consisting of more than 96 w/w % urea and less than 4 w/w % water. Thereafter the urea melt was particulated in a granulation process. The particles were collected and kept in an airtight bottle until the analyses were performed.
The crushing strength was determined by subjecting individual particles of urea of 3.15 mm to a measured force, applied by means of a metal plunger. The force, at which the particle fractures, was taken as a measure of strength. The average strength of 20 particles were reported.
The caking index was measured by the following procedure: An amount of particles was pressurized at 143 kgf (2 bar applied on a surface of 69.96 cm2) for 24 hrs at 270C. The lump of material was then taken out and broken, the amount of force (kgf) needed for this is taken as a measure for the caking tendency.
Dust formation in the products was measured by the following procedure: Clean air was blown through a glass spouted bed (85 mm in diameter) filled with 400 g of urea particles for 2 minutes at a flow rate of 25 Nm3/h. The dust formation is the weight loss of the product after the air treatment in the spouted bed.
Based on experience, the crushing strength should be > 3 kgf , the caking tendency should be < 75, and the dust formation should be < ~ 500 mg/kg.
Experiment 1
Different carbohydrates were added to the urea melt, and particulated as described above. The addition of carbohydrates was compared with urea without additive and with a standard product with urea-formaldehyde conditioning agent, UF80 (from Dynea, a mixture of urea/formaldehyde/water in a ratio of 23/57/20).
Table 1 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with different carbohydrates.
Table 1
Experiment 2
5 An aqueous polyvinyl alcohol) solution (12 % PVA with a degree of hydrolysis > 80 %) was obtained from Holland Novochem in the Netherlands. The carbohydrate was mixed into the aqueous polyvinyl alcohol) solution and the resulting aqueous solution of carbohydrate and polyvinyl alcohol) was added to the urea melt, where after the melt was particulated. The 0 added carbohydrates were fructose and HFS42, which is a commonly available syrup comprising 71 wt % dry matter and 29 wt % water, where the dry matter comprises 42 wt % fructose, 53 wt % dextrose, 2.5 wt % maltose, 1 wt % malotriose, and 1.5 wt % polysaccharides. The combinations of carbohydrate and polyvinyl alcohol) were compared with urea without 5 additive and the standard product with urea-formaldehyde conditioning agent, UF80.
Table 2 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with o different combinations of carbohydrate and polyvinyl alcohol).
Table 2
An aqueous polyvinyl alcohol) solution (12 % PVA with a degree of hydrolysis > 80 %) was obtained from Holland Novochem in the Netherlands. The carbohydrate was mixed into the aqueous polyvinyl alcohol) solution and the resulting aqueous solution of carbohydrate and polyvinyl alcohol) was added to the urea melt, where after the melt was particulated. The added carbohydrates were fructose and HFS42. The combinations of carbohydrate and polyvinyl alcohol) were compared with urea without additive and with the standard product with urea-formaldehyde, UF80. In this experiment, the concentration of the urea melt was more than 99 w/w % urea and less than 1 w/w % water.
Table 3 shows the crushing strength, dust formation and caking index for urea, without additive, with urea-formaldehyde conditioning agent and with different combinations of carbohydrates and polyvinyl alcohol).
Table 3
The additives according to the present invention can easily be added to the urea melt and do not require a preformed particle. The carbohydrates might be added to the urea melt as solids, they might be dissolved in a solvent or an aqueous solution of the polyvinyl compound or a urea solution before being added to the urea melt. The required amounts of the additives according to the present invention are lower than most other conditioning agents, and the toxicity is much lower than for the commonly used conditioning agent, formaldehyde.