[go: up one dir, main page]

WO2001077019A2 - Procede de production de nitrate de potassium - Google Patents

Procede de production de nitrate de potassium Download PDF

Info

Publication number
WO2001077019A2
WO2001077019A2 PCT/IL2001/000327 IL0100327W WO0177019A2 WO 2001077019 A2 WO2001077019 A2 WO 2001077019A2 IL 0100327 W IL0100327 W IL 0100327W WO 0177019 A2 WO0177019 A2 WO 0177019A2
Authority
WO
WIPO (PCT)
Prior art keywords
solution
nitrate
magnesium
ions
calcium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IL2001/000327
Other languages
English (en)
Other versions
WO2001077019A3 (fr
Inventor
Gregory Pipko
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NUTRITION AND GROWTH Ltd
Original Assignee
NUTRITION AND GROWTH Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NUTRITION AND GROWTH Ltd filed Critical NUTRITION AND GROWTH Ltd
Priority to AU50605/01A priority Critical patent/AU5060501A/en
Publication of WO2001077019A2 publication Critical patent/WO2001077019A2/fr
Publication of WO2001077019A3 publication Critical patent/WO2001077019A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00—Nitrates of sodium, potassium or alkali metals in general
    • C01D9/04—Preparation with liquid nitric acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00—Nitrates of sodium, potassium or alkali metals in general
    • C01D9/08—Preparation by double decomposition
    • C01D9/12—Preparation by double decomposition with nitrates or magnesium, calcium, strontium, or barium

Definitions

  • the present invention relates to a process for the production of potassium nitrate (KNO 3 ) by the salting-out of KNO 3 through cooling of a solution which essentially contains the ions K + , Cl , M ++ and N0 3 , wherein M ++ represents Ca " ⁇ and/or Mg ⁇ .
  • the process according to the present invention is carried out in aqueous phase and is characterized by the addition of calcium carbonate or magnesium carbonate or magnesium oxide or calcium oxide or magnesium hydroxide or calcium hydroxide or dolomite (Ca » MgC0 3 ), to aqueous solution of potassium chloride and nitric acid.
  • the addition of said minerals and cooling cause KNO 3 to crystallize and salt-out of the solution.
  • the M ++ and nitrate ions can be obtained from calcium nitrate and/or magnesium nitrate.
  • the potassium chloride is added to the mixture in the form of carnallite (KCl-MgCl 2 -6H 2 O), sylvinite (KCl-NaCl), and mixtures containing KC1 and CaCl 2 and/or MgCl 2 and/or NaCL
  • Potassium nitrate has various agricultural and industrial applications. It is a very important potassium fertilizer and is used extensively as raw material for the dying and explosive industries. It is also used in technical baths for elevated temperatures. Most of the potassium nitrate in the market is industrially manufactured.
  • reaction 2 does not result in KNO 3 precipitation but in a solution containing the ions K + , NO 3 , H + and Cl . Therefore, if the process is carried out in solution it is usually carried out with excess of nitric acid in order to drive the reaction forward, and additional materials and steps are needed to enable the precipitation of the desired mineral from the aqueous solution and to recycle the excess acid.
  • Such steps involve the addition of an organic phase such as disclosed in US4364914 and US437834 and GB2217700.
  • non-simple apparatus such as an apparatus for negative pressure and elevated temperatures as disclosed in CNl 064063, or a plurality of resin filled chambers as disclosed in US5110578 which is based on ion exchange method.
  • the present invention provides a simple and facile method for the preparation of potassium nitrate from potassium chloride and nitric acid in stoicheiometric ratio, which involves simple equipment and only abundant and low-cost raw materials.
  • the method according to present invention is carried out in aqueous phase without the addition of any organic solvent and without the need for sophisticated equipment.
  • the method for the preparation of potassium nitrate according to the present invention is based on salting out of potassium nitrate from an aqueous solution containing the ions K + , Cl , N0 3 and IVf ⁇ " , wherein Iv represents Ca " ⁇ and/or
  • the source of said ions is not important as long as approximately stoichometric ratio between the potassium and nitrate ions is obtained.
  • the minerals from which the solution is prepared can be selected according to their abundance and cost.
  • the present invention is characterized by the addition of carbonates or oxides or hydroxides of calcium or magnesium, or dolomite, or a combination thereof, (i.e, CaC0 3 or MgC0 3 or CaO or MgO or Ca(OH) 2 or Mg(OH) 2 or dolomite - CaC0 3 «MgC0 3 ) to a solution containing HNO 3 and KC1 in approximately stoicheiometric ratio.
  • the addition of these minerals which are all naturally occurred abundant minerals, causes, upon cooling, the precipitation of potassium nitrate from the solution.
  • KC1 can be added to the solution not as pure potassium chloride but as raw carnallite (KCl-MgCl 2 -6H 2 0) or sylvinite (KCl-NaCl), or mixtures containing KC1, and NaCl and/or MgCl 2 and/or CaCl 2 , which are very abundant natural occurring minerals and also the principal components of many salt deposits.
  • Sylvinite and carnallite are also a by-product in the salt in dustry and the last deposition in stage by stage evaporation in salt lakes such as in the Dead Sea.
  • Sylvinite and carnallite are one of the main sources for KC1 and using it as it is, without the need to firstly separate the KC1 provides a process which is simpler and saves costs and energy.
  • the M* ' and nitrate ions can be obtained from calcium nitrate and/or magnesium nitrate.
  • the present invention relates to a short and facile process for the preparation of potassium nitrate characterized by the preparation of an aqueous solution at temperature higher than 40 °C, containing the ions K + , Cl , M " " and N0 3 wherein M ++ represents Ca -* " and/or Mg ⁇ , and obtaining precipitate of the potassium nitrate by cooling said solution
  • the method of the present invention comprises the following steps:
  • step (b) dissolving at least one source for potassium chloride, in the solution obtained at step (a) at temperature higher than 40°C, wherein the amount of said source is chosen such as to obtain an approximately stoicheiometric ratio between potassium and nitrate ions and wherein said source is selected from the group consisting of KC1, carnallite, sylvinite, and a mixture of KC1 with MgCl 2 , NaCl, CaCl 2 or a combination thereof;
  • step (c) cooling the solution obtained at step (b) to obtain a precipitate of potassium nitrate.
  • the method according to the present invention can be carried out as a continuous process or in batch.
  • the concentration of the nitrate and potassium ions in the initial hot solution is in the range 0.5 to 8N, preferably in the range 3-6 N (N being the concentration in equivalents per liter solution).
  • the method according to the present invention can further comprise the production of magnesium chloride (MgCl 2 ) or of calcium chloride (CaCl 2 ) as a by-product from the filtrate solution obtained after the separation of KNO 3
  • the method according to the present invention is based on salting out of potassium nitrate from an aqueous solution containing approximately equivalent amounts of the ions K + , Cl , NO 3 and M “ " , wherein M " " represents Ca " ⁇ and/or
  • Mg "1-1" which results from oxides, hydroxides or carbonates of magnesium and/or calcium.
  • the first step to obtain such a solution is by dissolving carbonates or oxides or hydroxides of calcium or magnesium, or dolomite, in aqueous solution of HN0 3 ; followed by dissolving an equivalent amount of KC1.
  • Reactions 3 - 5 are exothermic reactions resulting in elevation of the solution temperature.
  • the aqueous solution contains the ions K + , Cl , Ca ++ and/or
  • the hot solution is filtered to filter out impurities and then cooled to 0 - 10°C,
  • the pure mineral usually of more than 96% purity, is obtained by separating from solution.
  • the potassium nitrate so obtained can be further purified by known techniques such as rinsing with water or with potassium nitrate solution, to obtained purity of more than 98% for use as fertilizer or by re-crystallization to obtain technical grade potassium nitrate with purity higher than 99.8%.
  • the first step of preparing the solution is by dissolving calcium nitrate and/or magnesium nitrate in water, then dissolving in the obtained solution a mineral or a mixture of minerals, being a source for potassium chloride in an amount which provides a solution of approximately equivalent concentrations of nitrate and potassium ions.
  • the source for the KC1 can be selected from KC1 of different purity grades, carnallite, sylvinite, or it can be a mixture of KC1 with MgCl 2 and/or NaCl and/or CaCl 2 .
  • HN0 3 HN0 3
  • dolomite powder (96% purity) was added to 102 g of 25% HN0 3 solution under continuous stirring.
  • 48 g of sylvinite (30 g KC1 + 15 g NaCl + 2 g H 2 0) were added to the dolomite hot solution (76-78°C) with continuous stirring. After the sylvinite dissolved completely, the solution was cooled to 6°C. 39.6 g of KN0 3 precipitate was obtained.
  • dolomite powder (96% purity) was added to 102 g of 25% HN0 3 solution under continuous stirring.
  • I l l g of carnallite (30 g KC1 + 38 g MgCl 2 + 43.2 g H 2 O) were added to the dolomite hot solution (80°C) with continuous stirring. After the carnallite dissolved completely, the solution was cooled to 20°C. 39 g of KNO 3 precipitate was obtained.
  • dolomite powder (94.7% purity) was added to 102 g of 25% HNO 3 solution under continuous stirring.
  • Examples 6-8, and 10-11 demonstrate that under appropriate conditions neither an excess of the ions Cl , M ++ , nor the presence of Na + , interfere with the process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Cette invention a trait à un procédé de production de nitrate de potassium par relargage à partir d'une solution aqueuse renfermant les ions K?+, C-, M++ et NO-¿3, M++ représentant Ca++ et/ou M++. Ce procédé consiste, (a), à dissoudre au moins un minéral choisi dans le groupe constitué par du carbonate de calcium, du carbonate de magnésium, de l'oxyde de magnésium, de l'oxyde de calcium, de l'hydroxyde de calcium, de l'hydroxyde de magnésium et par de la dolomite, dans de l'oxyde nitrique aqueux sous des quantités qui, du point de vue stoechiométrique, sont sensiblement équivalentes à la quantité des ions nitrate présents dans la solution, ou bien à dissoudre au moins un minéral choisi dans le groupe constitué par du nitrate de calcium et du nitrate de magnésium, dans de l'eau, (b), à dissoudre au moins une source de chlorure de potassium dans la solution obtenue lors de la phase (a) et ce, à une température supérieure à 40 °C, la quantité de la source étant calculée de manière à obtenir un rapport sensiblement stoechiométrique entre les ions de potassium et de nitrate. Cette source est choisie dans le groupe constitué par du KCl, de la carnallite, de la sylvinite ainsi que par un mélange de KCl et de MgC1¿2?, NaC1, CaC12 ou par leur combinaison et, (c), à refroidir la solution obtenue lors de la phase (b) afin d'obtenir un précipité de nitrate de potassium.
PCT/IL2001/000327 2000-04-12 2001-04-05 Procede de production de nitrate de potassium Ceased WO2001077019A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50605/01A AU5060501A (en) 2000-04-12 2001-04-05 A process for the production of potassium nitrate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL13561100A IL135611A0 (en) 2000-04-12 2000-04-12 A process for the production of potassium nitrate
IL135611 2000-04-12

Publications (2)

Publication Number Publication Date
WO2001077019A2 true WO2001077019A2 (fr) 2001-10-18
WO2001077019A3 WO2001077019A3 (fr) 2002-02-07

Family

ID=11074049

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2001/000327 Ceased WO2001077019A2 (fr) 2000-04-12 2001-04-05 Procede de production de nitrate de potassium

Country Status (3)

Country Link
AU (1) AU5060501A (fr)
IL (1) IL135611A0 (fr)
WO (1) WO2001077019A2 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301215C (zh) * 2005-02-25 2007-02-21 湖南理工学院 一种制取硝酸钾和氯化镁的工艺方法
CN1302992C (zh) * 2005-09-06 2007-03-07 张罡 氢氧化镁循环反应法制取硝酸钾方法
CN1318303C (zh) * 2005-08-08 2007-05-30 张罡 硝酸转化法制取硝酸钾方法
RU2393117C1 (ru) * 2008-12-22 2010-06-27 Закрытое акционерное общество "Завод "БИНИТ" Способ получения нитрата калия и хлорида магния из хлорида калия и нитрата магния
CN106629783A (zh) * 2016-10-13 2017-05-10 张宏善 一种硝酸钾的制备方法
CN110862101A (zh) * 2019-12-25 2020-03-06 安徽胜达化工科技有限公司 一种硝酸钾的制备方法
TWI716267B (zh) 2020-01-20 2021-01-11 中國石油化學工業開發股份有限公司 2,4-二苯碸基苯酚之純化方法
CN112875728A (zh) * 2021-02-07 2021-06-01 武汉世吉药业有限公司 一种高纯度硝酸钾的制备方法及高纯度硝酸钾

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108439435A (zh) * 2018-03-24 2018-08-24 山东天化学股份有限公司 一种直接法制备硝酸钾的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3433584A (en) * 1966-03-07 1969-03-18 St Paul Ammonia Products Inc Production of potassium nitrate from calcium nitrate
GB1313926A (en) * 1969-05-22 1973-04-18 Montedison Spa Preparation of potassium nitrate
IL53431A (en) * 1977-11-21 1980-12-31 Israel Chemicals Ltd Process for the production of potassium nitrate
CS276859B6 (sk) * 1990-08-09 1992-08-12 Anton Dipl Tech Pavlotty Sposob výroby dusičnanu draselného
CN1043750C (zh) * 1995-08-31 1999-06-23 夏文建 硝酸钾生产工艺

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1301215C (zh) * 2005-02-25 2007-02-21 湖南理工学院 一种制取硝酸钾和氯化镁的工艺方法
CN1318303C (zh) * 2005-08-08 2007-05-30 张罡 硝酸转化法制取硝酸钾方法
CN1302992C (zh) * 2005-09-06 2007-03-07 张罡 氢氧化镁循环反应法制取硝酸钾方法
RU2393117C1 (ru) * 2008-12-22 2010-06-27 Закрытое акционерное общество "Завод "БИНИТ" Способ получения нитрата калия и хлорида магния из хлорида калия и нитрата магния
CN106629783A (zh) * 2016-10-13 2017-05-10 张宏善 一种硝酸钾的制备方法
CN110862101A (zh) * 2019-12-25 2020-03-06 安徽胜达化工科技有限公司 一种硝酸钾的制备方法
TWI716267B (zh) 2020-01-20 2021-01-11 中國石油化學工業開發股份有限公司 2,4-二苯碸基苯酚之純化方法
CN113135847A (zh) * 2020-01-20 2021-07-20 中国石油化学工业开发股份有限公司 2,4-二苯砜基苯酚的纯化方法
CN112875728A (zh) * 2021-02-07 2021-06-01 武汉世吉药业有限公司 一种高纯度硝酸钾的制备方法及高纯度硝酸钾

Also Published As

Publication number Publication date
IL135611A0 (en) 2001-05-20
WO2001077019A3 (fr) 2002-02-07
AU5060501A (en) 2001-10-23

Similar Documents

Publication Publication Date Title
US6017500A (en) High purity lithium salts and lithium salt solutions
US7214355B2 (en) Production of lithium compounds directly from lithium containing brines
US6776972B2 (en) Recovery of common salt and marine chemicals from brine
US7390466B2 (en) Production of lithium compounds directly from lithium containing brines
US6936229B1 (en) Recovery of lithium compounds from brines
US20180320247A1 (en) Process for producing lithium carbonate from concentrated lithium brine
AU2002212675B2 (en) Recovery of sodium chloride and other salts from brine
KR20010034850A (ko) 황산칼륨 제조방법
WO2001077019A2 (fr) Procede de production de nitrate de potassium
JP2010222242A (ja) ブラインからの塩化ナトリウムおよび他の塩類の回収
CA2552104C (fr) Procede de recuperation de sulfate de potasse
CA2538493C (fr) Procede ameliore pour la recuperation de sulfate de potasse (sop) dans des eaux salees riches en sulfate
US3484195A (en) Selective recovery of salts from mixed salt solutions
CN102596856A (zh) 自杂卤石制备商业级质量的硝酸钾的方法
US6692716B1 (en) Method of formulating alkali earth salts
AU751236B2 (en) Method of formulating alkali metal salts
AU2010264079B2 (en) Polyhalite IMI process for KNO3 production
US3993729A (en) Process for the manufacture of potassium phosphates
JP7549056B2 (ja) リチウム抽出方法、炭酸リチウムの製造方法及び水酸化リチウムの製造方法
US20240367989A1 (en) Preparation of lithium carbonate and lithium hydroxide
Heikkinen Crystallisation of potassium sulphate from an industrial stream
CN104556154B (zh) 一种高盐水蒸发后残余液的综合利用工艺
WO2024031139A1 (fr) Procédé de récuperation de sulfate de potassium

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP