WO2003011754A1 - Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite) - Google Patents

Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite) Download PDF

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Publication number
WO2003011754A1
WO2003011754A1 PCT/US2002/024012 US0224012W WO03011754A1 WO 2003011754 A1 WO2003011754 A1 WO 2003011754A1 US 0224012 W US0224012 W US 0224012W WO 03011754 A1 WO03011754 A1 WO 03011754A1
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WIPO (PCT)
Prior art keywords
slurry
ammonium phosphate
magnesium ammonium
heating
monohydrate form
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Application number
PCT/US2002/024012
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French (fr)
Inventor
Warren D. Winterson
John F. Cunningham
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Philip Morris Products SA
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Philip Morris Products SA
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Priority to JP2003516953A priority Critical patent/JP4391229B2/en
Priority to EP02750346A priority patent/EP1421031A4/en
Publication of WO2003011754A1 publication Critical patent/WO2003011754A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C01B25/451—Phosphates containing plural metal, or metal and ammonium containing metal and ammonium

Definitions

  • the present invention relates to methods of producing magnesium ammonium phosphate in monohydrate form (dittmarite), and in particular to methods of converting a hexahydrate form of magnesium ammonium phosphate (struvite) into a monohydrate form of magnesium ammonium phosphate monohydrate (dittmarite).
  • Ammonium magnesium phosphate (AMP) monohydrate has been discovered as useful in producing reduced harm smoking articles.
  • Advantageous uses of AMP in smoking articles is described in commonly assigned U.S. Patent Application No. 09/399,159, which is incorporated herein by reference in its entirety.
  • the present invention provides a process for converting the more easily synthesized and stored AMP hexahydrate into monohydrate of high purity.
  • the resultant monohydrate (dittmarite) can then be either dried to stabilize it, or used directly in cigarette production such as paper making as filler or a filler component together with calcium carbonate.
  • a preferred embodiment of the present invention provides a process wherein AMP hexahydrate is heated under pressure to convert it to the monohydrate form.
  • an aqueous slurry of AMP hexahydrate is heated in a pressure vessel (e.g., autoclave) to 100°C to 110°C with agitation under pressures from 1 psig to 15 psig.
  • a pressure vessel e.g., autoclave
  • Table 1 sets forth parameters used in preparing high purity AMP monohydrate (dittmarite) by converting AMP hexahydrate (struvite) under elevated temperature and pressure. The test runs were carried out using an aqueous slurry having a solids content of 35 wt. % struvite in autoclave equipment available from Lee Industries in Philipsburg, PA.
  • Runs 2 and 3 exhibited higher purity (i.e. , higher conversion rates) results than Run 1, indicating the reaction should preferably be run at 105 °C and 12 to 15 psig.
  • the product of the reaction can be used as a slurry or the slurry can be dried to provide the dittmarite in particle form.
  • the dittmarite can be supplied directly to a tank in which the dittmarite is mixed with one or more components of the paper making feedstock, preferably at a temperature and/or pressure sufficient to maintain stability of the reaction product.
  • the overall process steps can include:
  • the pressure vessel has a jacket for heating and cooling, is rated for pressure operation, is of sanitary construction for easy clean up, and has at least one agitator, e.g. two agitators. One agitator scrapes the walls and creates a uniform temperature mixture, the second uses high shear to break up agglomerates and control particle size.
  • This vessel is a preferred embodiment of the invention due to its high degree of temperature uniformity, and ability to control particle size, a critical parameter of paper making. Details of operating such a vessel can include: Load drums of slurry into conversion vessel
  • the conversion process is preferably run without intentional venting of pressure, or unintentional leaks, as undesirable side reactions may occur and the purity of the resultant product is reduced.
  • the tank is in a filled condition during the conversion process.
  • the conversion process is effective to produce at least 95 % , preferably at least 95 % or 98 % or higher conversion of struvite to dittmarite. It is recognized that the initial slurry may contain additional ingredients and/or impurities that may be present provided such ingredients/impurities do not adversely affect the conversion process.
  • a slurry of up to 50% , preferably 20 to 40 weight % solids of hexahydrate form of magnesium ammonium phosphate is heated under pressure of up to 25 psig, preferably 10 to 15 psig, for time sufficient to convert at least 90%, preferably at least 95% , of the hexahydrate form of the magnesium ammonium phosphate to the monohydrate form thereof.
  • the slurry can be heated to 90 to 135°C, preferably 100 to 110°C, for at least 5 minutes, preferably 5 to 25 minutes, to effect the conversion to monohydrate magnesium ammonium phosphate.
  • the slurry can optionally be cooled but preferably not below a temperature at which the monohydrate magnesium ammonium phosphate will convert back to hexahydrate magnesium ammonium phosphate.
  • the slurry of monohydrate magnesium ammonium phosphate is preferably maintained above 55 °C, preferably above 60 °C until the slurry is further processed such as by incorporation into paper or by drying the slurry to obtain particles of magnesium ammonium phosphate.
  • FIG. 1 shows a layout of processing equipment suitable for effecting the conversion process and subsequent use of the dittmarite.
  • the monohydrate form of magnesium ammonium phosphate is desirable in paper making manufacture such as cigarette paper.
  • the slurry of the monohydrate form of magnesium ammonium phosphate can be mixed with feedstock of a paper making machine or the slurry can be dried to particle form (e.g. , powder) and such powder can be incorporated in the paper making feedstock.
  • particle form e.g. , powder
  • the struvite slurry hexahydrate magnesium ammonium phosphate can be obtained by any known processes of reacting magnesium hydroxide, ammonia, phosphoric acid and water.
  • the present invention provides an advantageous and effective method of converting such slurry of hexahydrate form to the monohydrate form of magnesium ammonium phosphate usable to form filler for paper making wherein a particle size is preferably in the range of approximately 2 m to 8 m, more preferably in the range of 2 ⁇ m to 4 ⁇ m. If the slurry is dried to particle form, a preferred spin-flash drier can be obtained from APV Anhydro of Tonawanda, New York.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

A process for converting the more easily synthesized and stored AMP hexahydrate into monohydrate of high purity. The resultant monohydrate (dittmarite) can then be either dried to stabilize it, or used directly in cigarette production such as paper making as filler or a filler component together with calcium carbonate.

Description

PROCESS OF PRODUCING MAGNESIUM AMMONIUM PHOSPHATE IN MONOHYDRATE FORM (DITTMARITE)
Field of the Invention
The present invention relates to methods of producing magnesium ammonium phosphate in monohydrate form (dittmarite), and in particular to methods of converting a hexahydrate form of magnesium ammonium phosphate (struvite) into a monohydrate form of magnesium ammonium phosphate monohydrate (dittmarite).
Background of the Invention Ammonium magnesium phosphate (AMP) monohydrate has been discovered as useful in producing reduced harm smoking articles. Advantageous uses of AMP in smoking articles is described in commonly assigned U.S. Patent Application No. 09/399,159, which is incorporated herein by reference in its entirety.
Summary of the Invention
The present invention provides a process for converting the more easily synthesized and stored AMP hexahydrate into monohydrate of high purity. The resultant monohydrate (dittmarite) can then be either dried to stabilize it, or used directly in cigarette production such as paper making as filler or a filler component together with calcium carbonate.
More particularly, a preferred embodiment of the present invention provides a process wherein AMP hexahydrate is heated under pressure to convert it to the monohydrate form. In a preferred process, an aqueous slurry of AMP hexahydrate is heated in a pressure vessel (e.g., autoclave) to 100°C to 110°C with agitation under pressures from 1 psig to 15 psig. Detailed Description of the Preferred Embodiments
Table 1 sets forth parameters used in preparing high purity AMP monohydrate (dittmarite) by converting AMP hexahydrate (struvite) under elevated temperature and pressure. The test runs were carried out using an aqueous slurry having a solids content of 35 wt. % struvite in autoclave equipment available from Lee Industries in Philipsburg, PA.
TABLE 1
Figure imgf000004_0001
Runs 2 and 3 exhibited higher purity (i.e. , higher conversion rates) results than Run 1, indicating the reaction should preferably be run at 105 °C and 12 to 15 psig. The product of the reaction can be used as a slurry or the slurry can be dried to provide the dittmarite in particle form. In a paper making operation, the dittmarite can be supplied directly to a tank in which the dittmarite is mixed with one or more components of the paper making feedstock, preferably at a temperature and/or pressure sufficient to maintain stability of the reaction product. In a cigarette paper making process, the overall process steps can include:
Premix drums of struvite slurry
1
Load drums of slurry into conversion vessel
1
Run conversion process
1
Pump out of conversion vessel into hot surge tank Pump dittmarite solution to paper making process The pressure vessel has a jacket for heating and cooling, is rated for pressure operation, is of sanitary construction for easy clean up, and has at least one agitator, e.g. two agitators. One agitator scrapes the walls and creates a uniform temperature mixture, the second uses high shear to break up agglomerates and control particle size. This vessel is a preferred embodiment of the invention due to its high degree of temperature uniformity, and ability to control particle size, a critical parameter of paper making. Details of operating such a vessel can include: Load drums of slurry into conversion vessel
I Start steam flow to vessel jacket to heat vessel and start vessel agitators
1 Heat the mixture to the target temperature I
Hold at target temperature I Pump resultant product to paper making machine or to spin flash drier The conversion process is preferably run without intentional venting of pressure, or unintentional leaks, as undesirable side reactions may occur and the purity of the resultant product is reduced. Preferably the tank is in a filled condition during the conversion process. The conversion process is effective to produce at least 95 % , preferably at least 95 % or 98 % or higher conversion of struvite to dittmarite. It is recognized that the initial slurry may contain additional ingredients and/or impurities that may be present provided such ingredients/impurities do not adversely affect the conversion process.
In a preferred process, a slurry of up to 50% , preferably 20 to 40 weight % solids of hexahydrate form of magnesium ammonium phosphate is heated under pressure of up to 25 psig, preferably 10 to 15 psig, for time sufficient to convert at least 90%, preferably at least 95% , of the hexahydrate form of the magnesium ammonium phosphate to the monohydrate form thereof. The slurry can be heated to 90 to 135°C, preferably 100 to 110°C, for at least 5 minutes, preferably 5 to 25 minutes, to effect the conversion to monohydrate magnesium ammonium phosphate. The slurry can optionally be cooled but preferably not below a temperature at which the monohydrate magnesium ammonium phosphate will convert back to hexahydrate magnesium ammonium phosphate. Thus, the slurry of monohydrate magnesium ammonium phosphate is preferably maintained above 55 °C, preferably above 60 °C until the slurry is further processed such as by incorporation into paper or by drying the slurry to obtain particles of magnesium ammonium phosphate. FIG. 1 shows a layout of processing equipment suitable for effecting the conversion process and subsequent use of the dittmarite.
The monohydrate form of magnesium ammonium phosphate is desirable in paper making manufacture such as cigarette paper. The slurry of the monohydrate form of magnesium ammonium phosphate can be mixed with feedstock of a paper making machine or the slurry can be dried to particle form (e.g. , powder) and such powder can be incorporated in the paper making feedstock. In order to prevent the magnesium ammonium phosphate in the monohydrate form from transforming back to the hexahydrate form, it is desirable to maintain the slurry above 55 °C until it is incorporated directly in feedstock (preferably heated above 60 °C) of the paper making machine or until the slurry is dried into particle form such as by flash drying which removes the water from the slurry under elevated temperature conditions. Once dry, the monohydrate form of the magnesium ammonium phosphate remains stable. The struvite slurry hexahydrate magnesium ammonium phosphate can be obtained by any known processes of reacting magnesium hydroxide, ammonia, phosphoric acid and water. The present invention provides an advantageous and effective method of converting such slurry of hexahydrate form to the monohydrate form of magnesium ammonium phosphate usable to form filler for paper making wherein a particle size is preferably in the range of approximately 2 m to 8 m, more preferably in the range of 2μm to 4μm. If the slurry is dried to particle form, a preferred spin-flash drier can be obtained from APV Anhydro of Tonawanda, New York.
While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made, and equivalents employed, without departing from the scope of the appended claims.

Claims

What is claimed is:
1. A process of making a monohydrate form of magnesium ammonium phosphate comprising: heating a slurry comprising a hexahydrate form of magnesium ammonium phosphate under pressure for a time sufficient to convert the hexahydrate magnesium ammonium phosphate to the monohydrate form thereof.
2. The process as claimed in Claim 1, further comprising agitation of the slurry.
3. The process as claimed in Claims 1, wherein the slurry is heated to a temperature up to 150 °C under a pressure of up to 100 psig.
4. The process as claimed in Claims 1, wherein the slurry is heated to a temperature of 100°C to 110°C under a pressure of about 10 to 15 psig.
5. The process as claimed in Claims 1, further comprising drying the slurry.
6. The process as claimed in Claim 5, wherein the drying step is conducted with a spin-flash drier.
7. The process as claimed in Claim 1, wherein the heating is carried out for a time sufficient to convert at least 95 % of the magnesium ammonium phosphate in hexahydrate form to the monohydrate form thereof.
8. The process as claimed in Claim 1, wherein subsequent to the heating step the process further comprises cooling the slurry to a temperature above
55°C.
9. The process as claimed in Claim 1, wherein the slurry includes 20 to 40 weight % of solids content prior to the heating step.
10. The process as claimed in Claim 1, wherein the slurry is contained in a sealed vessel during the heating step.
11. The process as claimed in Claim 10, wherein the slurry is subjected to stirring during the heating step.
12. The process as claimed in Claim 1, wherein subsequent to the heating step the slurry containing the monohydrate form of the magnesium ammonium phosphate is mixed with paper making feedstock during a paper making process.
13. The process as claimed in Claim 12, the paper making process is a cigarette making process.
14. The process as claimed in Claim 1, wherein the heating is carried out for at least 5 minutes.
15. The process as claimed in Claim 1 , wherein the heating is carried out for at least 10 minutes.
16. The process as claimed in Claim 1, wherein the heating is carried out for at least 15 minutes.
17. The process as claimed in Claim 1, wherein the slurry prior to the heating step has an average particle size of 4 to 7 m and/or the slurry has a pH of at least 7.
18. The product produced according to the process of Claim 1.
19. The product produced according to the process of Claim 5.
20. The product produced according to the process of Claim 13.
PCT/US2002/024012 2001-08-01 2002-07-30 Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite) Ceased WO2003011754A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2003516953A JP4391229B2 (en) 2001-08-01 2002-07-30 Method for producing monohydrate ammonium magnesium phosphate (Ditmalite)
EP02750346A EP1421031A4 (en) 2001-08-01 2002-07-30 Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite)

Applications Claiming Priority (4)

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US30886501P 2001-08-01 2001-08-01
US60/308,865 2001-08-01
US10/201,910 2002-07-25
US10/201,910 US7052581B2 (en) 2001-08-01 2002-07-25 Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1685855A4 (en) * 2003-11-14 2008-04-30 Idemitsu Technofine Co Ltd DEODORIZER AND DEODORIZING ARTICLE
WO2013055279A1 (en) 2011-10-13 2013-04-18 Ekobalans Fenix Ab Dewatering of phosphate precipitates

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7182872B2 (en) * 2003-08-01 2007-02-27 Wisconsin Alumni Research Foundation Struvite crystallization
US20050279475A1 (en) * 2004-01-30 2005-12-22 Philip Morris Usa Inc. Processes of making monohydrate form of magnesium ammonium phosphate and processes of making cigarette paper using same

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US3348910A (en) * 1963-11-29 1967-10-24 Dow Chemical Co Process for the manufacture of magnesium ammonium phosphate monohydrate
US4777026A (en) * 1983-08-25 1988-10-11 Thomas Griffith Production of phosphates from alkali-processes phosphate rock
US5294348A (en) * 1990-11-26 1994-03-15 Societe Nationale Elf Aquitaine Process for removing ammonia from waste waters
US5374294A (en) * 1993-05-19 1994-12-20 The Vigoro Corporation Controlled release potassium divalent metal phosphate fertilizer
US20020114753A1 (en) * 2000-08-17 2002-08-22 Green J. Richard Magnesium ammonium phosphate hexahydrate and monohydrate slurries

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US3285731A (en) * 1963-07-22 1966-11-15 Grace W R & Co Magnesium potassium phosphate-containing fertilizer and process
US3348910A (en) * 1963-11-29 1967-10-24 Dow Chemical Co Process for the manufacture of magnesium ammonium phosphate monohydrate
US4777026A (en) * 1983-08-25 1988-10-11 Thomas Griffith Production of phosphates from alkali-processes phosphate rock
US5294348A (en) * 1990-11-26 1994-03-15 Societe Nationale Elf Aquitaine Process for removing ammonia from waste waters
US5374294A (en) * 1993-05-19 1994-12-20 The Vigoro Corporation Controlled release potassium divalent metal phosphate fertilizer
US20020114753A1 (en) * 2000-08-17 2002-08-22 Green J. Richard Magnesium ammonium phosphate hexahydrate and monohydrate slurries

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1685855A4 (en) * 2003-11-14 2008-04-30 Idemitsu Technofine Co Ltd DEODORIZER AND DEODORIZING ARTICLE
WO2013055279A1 (en) 2011-10-13 2013-04-18 Ekobalans Fenix Ab Dewatering of phosphate precipitates
EP2766301A4 (en) * 2011-10-13 2015-06-24 Ekobalans Fenix Ab DEHYDRATION OF PHOSPHATE PRECIPITATES

Also Published As

Publication number Publication date
US7052581B2 (en) 2006-05-30
JP2005503310A (en) 2005-02-03
JP4391229B2 (en) 2009-12-24
EP1421031A1 (en) 2004-05-26
US20030056913A1 (en) 2003-03-27
EP1421031A4 (en) 2009-08-05

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