WO2014154189A1 - A method of production of potassium nitrate by electrodialysis and apparatus for making the same - Google Patents

A method of production of potassium nitrate by electrodialysis and apparatus for making the same Download PDF

Info

Publication number
WO2014154189A1
WO2014154189A1 PCT/CZ2014/000030 CZ2014000030W WO2014154189A1 WO 2014154189 A1 WO2014154189 A1 WO 2014154189A1 CZ 2014000030 W CZ2014000030 W CZ 2014000030W WO 2014154189 A1 WO2014154189 A1 WO 2014154189A1
Authority
WO
WIPO (PCT)
Prior art keywords
exchange
solution
anion
nitrate
exchange membrane
Prior art date
Application number
PCT/CZ2014/000030
Other languages
English (en)
French (fr)
Inventor
Lubomir MACHUCA
Ales CERNÍN
Original Assignee
Membrain S.R.O.
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 Membrain S.R.O. filed Critical Membrain S.R.O.
Publication of WO2014154189A1 publication Critical patent/WO2014154189A1/en

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
    • C01D9/08—Preparation by double decomposition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/50—Stacks of the plate-and-frame type
    • 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
    • C01D9/10—Preparation by double decomposition with ammonium nitrate
    • 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
    • C01D9/14—Preparation by double decomposition of salts of potassium with sodium nitrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/14—Specific spacers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/28—Specific concentration chambers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/30—Specific dilution or de-ionizing chambers

Definitions

  • the invention concerns a method of production of potassium nitrate by means of electrodialysis, consisting in the exchange of ions between solution of potassium chloride and solution of ammonium nitrate, nitric acid or sodium nitrate.
  • the invention also concerns a apparatus to perform this method.
  • the produced potassium nitrate has a wide range of use: in agriculture as a fertilizer, in glassmaking and in production of explosives and pyrotechnics, in food-processing industry as a preservative or in pharmacy as an ingredient in toothpastes.
  • KN0 3 Potassium nitrate
  • NaN0 3 sodium nitrate
  • HN0 3 nitric acid
  • NNLN0 3 ammonium nitrate
  • the method of production of potassium nitrate by means of electrodialysis contributes to resolving these disadvantages while keeping the progressive features of the electrolytic process.
  • the principle of the invention consists in the fact that the exchange of ions between solution of potassium chloride and solution of ammonium nitrate, nitric acid or sodium nitrate occurs in electric field in a system of ion-exchange membranes, containing at least one sequence of anion-exchange membranes and cation-exchange membranes, alternating and creating at least four intermembrane spaces.
  • solutions of the said chemical compounds flow in the following manner: solution of input potassium chloride flows in the first intermembrane space before the first anion- exchange membrane; solution of ammonium nitrate, nitric acid or sodium nitrate flows in the third intermembrane space between the first cation-exchange membrane and the second anion-exchange membrane.
  • Solution of the main product - potassium nitrate - flows in the fourth intermembrane space between the second anion-exchange membrane and the second cation-exchange membrane, and solution of by-product - ammonium chloride, hydrochloric acid or sodium chloride - flows in the second intermembrane space between the first anion- exchange membrane and the first cation-exchange membrane.
  • the concentrations of input solutions of potassium chloride and ammonium nitrate, nitric acid or sodium nitrate should be between 0.01 and 0.3 mol/L, and the concentration of output solutions of products - potassium nitrate and ammonium chloride, hydrochloric acid or sodium chloride - is higher than 1 mol/L.
  • the operating temperature of solutions should range between 10 and 80 °C, preferably between 20 and 50 °C.
  • the device to perform the method according to the invention consists of electrodes, between which there is a system of ion-exchange membranes, containing at least one sequence of anion-exchange membranes and cation-exchange membranes, alternating and creating at least four intermembrane spaces (CI, C2, Dl, D2) for solutions of input and output chemical compounds of the dialytic exchange of ions.
  • Ion-exchange membranes should be of a homogeneous or heterogeneous type with the thickness of 0.1 to 1 mm and permselectivity of more than 90%, and between them there are spacers with the thickness of 0.1 to 2 mm, made of polymeric material to secure distribution and mutual non-mixing of solutions, and mechanical support of intermembrane spaces.
  • the voltage between electrodes should range between 0.5 to 2 V on the sequence of four membranes - membrane quadruplet - with current density from 40 to 400 A/m 2 .
  • Advantages of the method of obtaining potassium nitrate according to the invention consist in getting a highly purified K O 3 solution with a high level of conversion.
  • the conversion itself occurs in the device of electrodialyser, made of noncorrosive components based on polymeric materials.
  • Fig. 1 shows the functional scheme of the method of production of potassium nitrate by means of electrodialysis on one (basic) sequence of ion-exchange membranes
  • Fig. 2 shows an example of arrangement of five sequences of four membranes - membrane quadruplets.
  • the laboratory unit P EDR-Z/4x (by the MemBrain company) for electrodialysis- metathesis was used (hereafter only EDM).
  • the unit contained 5 tanks with the volumes from 0.25 to 2 litres and 5 centrifugal pumps with magnetic inserts for circulation of solution in intermembrane spaces CI , C2, D_i, D2, created by sequences of anion-exchange membranes AMI, AM2 and cation-exchange membranes CM1, CM2 (for a scheme of one basic sequence, see Fig. 1).
  • these were the following solutions: • diluate 1 - solution of input potassium chloride (KC1), flowing through the first intermembrane space Dl before the first anion-exchange membrane AMI,
  • the unit was equipped with tools to measure flow rates, temperature, conductivity and pH for each individual circuit and with direct current supply with the output of 90 W.
  • the EDM module was equipped with 11 cation-exchange membranes CM (RALEX CM-PES) and 10 anion-exchange membranes AM (RALEX AM-PES), alternating and creating 5 sequences of membranes (quadruplets) - see the scheme in Fig. 2. Each of these sequences was arranged according to Fig. 1. The effective area of one membrane was 64 cm 2 .
  • the test was performed analogously and on a device similar to Example 1, but in a continuous manner with recycling (feed and bleed).
  • the testing unit was supplemented with 2 external tanks for concentrated solutions of KCl and NH 4 N0 3 and 2 peristaltic pumps. Suction of peristaltic pumps was from the external tanks and outlet was connected to working circuits of KCl or ⁇
  • solution of KCl was added with concentration 0.2 mol L.
  • NH 4 N0 3 third intermembrane space D2 with concentration 0.03 mol/L
  • solution of ⁇ 3 ⁇ 4 ⁇ 0 3 was added with concentration 0.2 mol/L.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
PCT/CZ2014/000030 2013-03-28 2014-03-21 A method of production of potassium nitrate by electrodialysis and apparatus for making the same WO2014154189A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2013-234 2013-03-28
CZ2013-234A CZ2013234A3 (cs) 2013-03-28 2013-03-28 Způsob výroby dusičnanu draselného metodou elektrodialýzy a zařízení k provádění tohoto způsobu

Publications (1)

Publication Number Publication Date
WO2014154189A1 true WO2014154189A1 (en) 2014-10-02

Family

ID=50687223

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CZ2014/000030 WO2014154189A1 (en) 2013-03-28 2014-03-21 A method of production of potassium nitrate by electrodialysis and apparatus for making the same

Country Status (2)

Country Link
CZ (1) CZ2013234A3 (cs)
WO (1) WO2014154189A1 (cs)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104261435A (zh) * 2014-10-10 2015-01-07 山东诺贝丰化学有限公司 一种复分解法硝酸钾结晶系统及结晶工艺
CN112723390A (zh) * 2021-02-03 2021-04-30 浙江艺谛环境设备有限公司 一种氯化钠与碳酸氢铵制备碳酸氢钠与氯化铵的处理系统及工艺

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465568A (en) 1981-11-16 1984-08-14 Olin Corporation Electrochemical production of KNO3 /NaNO3 salt mixture
WO1986006646A1 (en) * 1985-05-03 1986-11-20 Allied Corporation Recovery of mixed acids from mixed salts
US4995950A (en) 1987-09-04 1991-02-26 Basf Aktiengesellschaft Preparation of alkali metal nitrates
CA2027064A1 (en) 1989-10-05 1991-04-06 Alvaro Abidaud Continuous production of potassium nitrate via ion exchange
US5110578A (en) * 1989-10-05 1992-05-05 Monomeros Colombo Venezolanos, S.A. (E.M.A.) Continuous production of potassium nitrate via ion exchange
US5207879A (en) * 1991-03-11 1993-05-04 The Graver Company Bipolar membrane stack and method for production of low chloride sodium hydroxide
CN1122793A (zh) 1994-11-05 1996-05-22 张辉 副产氮钾二元复合肥的生产方法
CN1184077A (zh) 1996-12-06 1998-06-10 陈淑奇 离子交换法生产硝酸钾工艺
EP1235743A1 (en) 1999-12-03 2002-09-04 Kemira Agro Oy Production of two alkali metal salts by a combined ion exchange and crystallisation process
CN1827526A (zh) 2005-08-31 2006-09-06 东华工程科技股份有限公司 一种复分解法制备硝酸钾的方法
CN101628723A (zh) 2009-08-18 2010-01-20 湖南丹化农资有限公司 复分解反应生产硝酸钾和氯化铵的方法
CN101973564A (zh) 2010-11-01 2011-02-16 赵家春 烟花爆竹用硝酸钾及其制备方法
EP2418171A1 (en) * 2006-01-06 2012-02-15 Nextchem Method for increasing the hydroxide content of polymetal hydroxychlorides used as antiperspirant salt compositions with enhanced efficacy

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4253929A (en) * 1980-03-05 1981-03-03 Philip Morris Incorporated Method for denitration of tobacco employing electrodialysis
CH677325A5 (cs) * 1989-04-28 1991-05-15 Asea Brown Boveri
JP3198297B2 (ja) * 1992-11-27 2001-08-13 経済産業省産業技術総合研究所長 苛性ソーダの製造方法
JP5072477B2 (ja) * 2007-08-10 2012-11-14 株式会社アストム 硝フッ酸廃液からの酸の回収方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465568A (en) 1981-11-16 1984-08-14 Olin Corporation Electrochemical production of KNO3 /NaNO3 salt mixture
WO1986006646A1 (en) * 1985-05-03 1986-11-20 Allied Corporation Recovery of mixed acids from mixed salts
US4995950A (en) 1987-09-04 1991-02-26 Basf Aktiengesellschaft Preparation of alkali metal nitrates
CA2027064A1 (en) 1989-10-05 1991-04-06 Alvaro Abidaud Continuous production of potassium nitrate via ion exchange
US5110578A (en) * 1989-10-05 1992-05-05 Monomeros Colombo Venezolanos, S.A. (E.M.A.) Continuous production of potassium nitrate via ion exchange
US5207879A (en) * 1991-03-11 1993-05-04 The Graver Company Bipolar membrane stack and method for production of low chloride sodium hydroxide
CN1122793A (zh) 1994-11-05 1996-05-22 张辉 副产氮钾二元复合肥的生产方法
CN1184077A (zh) 1996-12-06 1998-06-10 陈淑奇 离子交换法生产硝酸钾工艺
EP1235743A1 (en) 1999-12-03 2002-09-04 Kemira Agro Oy Production of two alkali metal salts by a combined ion exchange and crystallisation process
CN1827526A (zh) 2005-08-31 2006-09-06 东华工程科技股份有限公司 一种复分解法制备硝酸钾的方法
EP2418171A1 (en) * 2006-01-06 2012-02-15 Nextchem Method for increasing the hydroxide content of polymetal hydroxychlorides used as antiperspirant salt compositions with enhanced efficacy
CN101628723A (zh) 2009-08-18 2010-01-20 湖南丹化农资有限公司 复分解反应生产硝酸钾和氯化铵的方法
CN101973564A (zh) 2010-11-01 2011-02-16 赵家春 烟花爆竹用硝酸钾及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104261435A (zh) * 2014-10-10 2015-01-07 山东诺贝丰化学有限公司 一种复分解法硝酸钾结晶系统及结晶工艺
CN104261435B (zh) * 2014-10-10 2015-12-02 诺贝丰（中国）化学有限公司 一种复分解法硝酸钾结晶系统及结晶工艺
CN112723390A (zh) * 2021-02-03 2021-04-30 浙江艺谛环境设备有限公司 一种氯化钠与碳酸氢铵制备碳酸氢钠与氯化铵的处理系统及工艺

Also Published As

Publication number Publication date
CZ304507B6 (cs) 2014-06-04
CZ2013234A3 (cs) 2014-06-04

Similar Documents

Publication Publication Date Title
Han et al. Preparation of chloride-free potash fertilizers by electrodialysis metathesis
Lopez et al. Potential of electrodialytic techniques in brackish desalination and recovery of industrial process water for reuse
CN103864249B (zh) 一种由盐湖卤水提取氢氧化锂的方法
Greiter et al. Desalination of whey by electrodialysis and ion exchange resins: analysis of both processes with regard to sustainability by calculating their cumulative energy demand
Melnikov et al. Study of electrodialysis concentration process of inorganic acids and salts for the two-stage conversion of salts into acids utilizing bipolar electrodialysis
Kabay et al. Effect of feed characteristics on the separation performances of monovalent and divalent salts by electrodialysis
CN103882468B (zh) 一种由碳酸锂生产氢氧化锂的电解-双极膜电渗析系统及其生产方法
Qiu et al. Sustainable recovery of high-saline papermaking wastewater: Optimized separation for salts and organics via membrane-hybrid process
Zhuang et al. Zero discharge process for foil industry waste acid reclamation: Coupling of diffusion dialysis and electrodialysis with bipolar membranes
Sadrzadeh et al. Mathematical modeling of desalination by electrodialysis
Zhang et al. Continuous synthesis of high purity KNO3 through electrodialysis metathesis
WO2019228577A2 (en) Process for preparing lithium chemical compounds by electrodialysis method and apparatus for performing this process
Graillon et al. Development of electrodialysis with bipolar membrane for the treatment of concentrated nitrate effluents
Feng et al. Techno-economic evaluation of preparing high-valued TPAOH from its low-cost bromide via electrodialysis metathesis (EDM)
Kabay et al. Effect of salt combination on separation of monovalent and divalent salts by electrodialysis
CN105056763B (zh) 无电压双膜渗析脱除水中盐分的方法和反应器
CN108698862B (zh) 通过电解处理工业废水的方法
WO2014154189A1 (en) A method of production of potassium nitrate by electrodialysis and apparatus for making the same
Zhang et al. Conversion of potassium chloride into potassium sulfate by four-compartment electrodialysis: batch operation process
Li et al. Synchronously recovering different nutrient ions from wastewater by using selective electrodialysis
US3616385A (en) Chlorine- and chloride-free hyprochlorous acid by electrodialysis
Greiter et al. Electrodialysis versus ion exchange: comparison of the cumulative energy demand by means of two applications
Strathmann et al. Electromembrane processes, efficient and versatile tools in a sustainable industrial development
Mitko et al. Innovations in electromembrane processes
Harrison The electrodialysis of lithium sulphate to lithium hydroxide

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14722982

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14722982

Country of ref document: EP

Kind code of ref document: A1