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WO1990011119A2 - Separation d'acetate d'ammonium et d'hydroxyde d'ammonium au moyen d'une membrane - Google Patents

Separation d'acetate d'ammonium et d'hydroxyde d'ammonium au moyen d'une membrane Download PDF

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Publication number
WO1990011119A2
WO1990011119A2 PCT/CA1990/000089 CA9000089W WO9011119A2 WO 1990011119 A2 WO1990011119 A2 WO 1990011119A2 CA 9000089 W CA9000089 W CA 9000089W WO 9011119 A2 WO9011119 A2 WO 9011119A2
Authority
WO
WIPO (PCT)
Prior art keywords
support member
porous hollow
hollow support
membrane
separation
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/CA1990/000089
Other languages
English (en)
Other versions
WO1990011119A3 (fr
Inventor
Ying Wang
Qilian Yang
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.)
International Applied Sciences Inc
Original Assignee
International Applied Sciences Inc
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 International Applied Sciences Inc filed Critical International Applied Sciences Inc
Priority to AU53356/90A priority Critical patent/AU5335690A/en
Publication of WO1990011119A2 publication Critical patent/WO1990011119A2/fr
Publication of WO1990011119A3 publication Critical patent/WO1990011119A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/364—Membrane distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/10—Separation of ammonia from ammonia liquors, e.g. gas liquors

Definitions

  • This invention generally relates to the field of separation technology and more particularly to membrane distillation of liquids.
  • the present invention provides a separation member for use in the separation of ammonium acetate and ammonium hydroxide from a liquid containing same comprising a porous hollow support member and a membrane which is integrally associated with the porous hollow support member, the membrane having been formed by subjecting the porous hollow support member to a solution containing an effective amount of a polysiloxane and a silane and if required a crosslinking agent, for a period of time sufficient to form a membrane integrally associated with the porous hollow support member and which is capable of separating ammonium acetate and ammonium hydroxide from the liquid.
  • the invention also provides a process for the preparation of a separation member for use in the separation of ammonium acetate and ammonium hydroxide from a liquid containing same which comprises providing a porous hollow support member and forming a membrane which is integrally associated with the porous hollow support member by subjecting the porous hollow support member to a solution containing an effective amount of a polysiloxane and a silane and if required a crosslinking agent for a period of time sufficient to form a membrane integrally associated with the porous hollow support member and which is capable of separating ammonium acetate and ammonium hydroxide from the liquid.
  • the invention further provides a membrane module for use in the separation of ammonium acetate and ammonium hydroxide from a liquid containing same containing one or more of the separation members of the invention as described .above.
  • Figure 1 is a schematic diagram of a process for separating ammonium acetate and ammonium hydroxide from a liquid.
  • the invention provides a separation member for use in the separation of ammonium acetate and ammonium hydroxide from a liquid containing same comprising a porous hollow support member and a membrane which is integrally associated with the porous hollow support member, the membrane having been formed by subjecting the porous hollow support member to a solution containing an effective amount of a polysiloxane and a silane, and if required a crosslinking agent, for a period of time sufficient to form a membrane integrally associated with the porous hollow support member and which is capable of separating ammonium acetate and ammonium hydroxide from the liquid.
  • a process for the preparation of a separation member for use in the separation of ammonium acetate and ammonium hydroxide from a liquid comprises providing a porous hollow support member and forming a membrane which is integrally associated with the porous hollow support member.
  • the membrane is formed by subjecting the porous hollow support member to an effective amount of a solution containing a polysiloxane and a silane and if required a crosslinking agent for a period of time sufficient to form a membrane integrally associated with the porous hollow support member, and which is capable of separating ammonium acetate and ammonium hydroxide.
  • the porous hollow support member has an outside diameter of from 50 to 3000 microns and a wall thickness of from 10 to 200 microns.
  • the pore size of the porous hollow support member is about .01 to 5 microns.
  • the porous hollow support member used in the present invention is typically made from methyl cellulose, ethyl cellulose. acetyl cellulose or polysulfone.
  • the porous hollow support member may be a commercially available microporous hollow fiber.
  • a membrane is formed on the inner and/or outer surfaces and within the interstices of the pores of the porous hollow support member by subjecting the porous hollow support member to a solution containing an effective amount of a polysiloxane and a silane, and if required, a crosslinking agent for a period of time sufficient to form a membrane capable of separating ammonium acetate and ammonium hydroxide.
  • the membrane may be formed by preparing a solution containing polysiloxane and silane in an organic solvent.
  • polydi ethyl siloxane may be used as the polysiloxane and o-dimethyl-hydroxyl-silane may be used as the silane.
  • Suitable organic solvents which may be used include gasoline, methyl alcohol and cyclohexane.
  • the solution contains about 0.5-30% of the polysiloxane and about 2-35% of the silane, preferably 5-15%.
  • Polycondensation of polysiloxane and silane occurs in the presence of a crosslinking agent such as n-hexylamine-2- ethyl sodium acetate which may accelerate hydrolysis.
  • a crosslinking agent for example, n-hexylamine-2- ethyl sodium acetate may be used in the solution for forming the membrane.
  • Other crosslinking agents which may be used include tetraethyl orthosilicate.
  • the polysiloxane/silane solution is passed through and about in contact with the surfaces of the porous hollow support member cyclically from inside to outside and/or outside to inside of the porous hollow support member for from 5 to 120 minutes at a rate of about 10 to 30 cm 2 /sec. and a pressure of about 0.5 to 1 Kg/cm 2 .
  • the solution is then discharged from the system. Once the solution has been discharged, the separation member is dried under reduced pressure at 40 to 90° C. for from one to ten hours to complete production of the separation member.
  • the resulting membrane which is integrally associated with the porous hollow support member is hydrophobic and has a pore size of about 10A to lOOOA, a thickness of about 1 to 50 microns.
  • the invention also provides a membrane module containing one or more separation members.
  • Commercially available modules are typically used such as those sold under the name Calyx Capsules by Micron Separations Inc. and under the name PM by Romicon.
  • the diameter of the membrane module of the invention containing one or more of the separation members is about 0.025 to 0.3 metres and has a length of about .25 to 6 metres.
  • the membrane is formed on the porous hollow support members by subjecting a membrane module containing the porous hollow support members to a solution containing an effective amount of a polysiloxane and silane using the process described above.
  • the invention also provides a method for the distillation separation of ammonium acetate and ammonium hydroxide from a liquid containing same using one or more separation members of the invention.
  • the method of the invention may be used to separate ammonium acetate and ammonium hydroxide from liquids such as liquid effluents and groundwaters including industiral wastewater or groundwater containing ammonium acetate and ammonium hydroxide.
  • Hot wastewater typically having temperatures in the range 50°C to 90°C
  • ammonium hydroxide typically at a concentration of about 0.5 to 5% by volume and ammonium acetate typically at a concentration of about 0.5 to 8% by volume enters the membrane module 5 at entrance A.
  • the membrane module 5 contains porous hollow support members 12 extending therealong. The interior of the module fluidly communicates with the caps 14 located at either end of the module 5. The exterior portions of the porous hollow support members 12 are fluidly isolated from the caps 14 by seals 16.
  • the hot fluid entering at A passes across the exterior surfaces of the porous hollow support members 12 and exits at B.
  • a pump 8 pumps relatively cold air (typically having a temperatures in the range of about 0°C to 45°C) through one of the membrane module caps 14 at entrance C.
  • the cold air passes along the interior of the porous hollow support members 12 and exits from the opposite cap 14 at D.
  • the membrane integrally associated with the porous hollow support members 12 is hydrophobic, the temperature difference between the exterior and interior surfaces of the hollow support members 12 will result in different saturation vapour pressures in the interior and exterior of the porous hollow support members 12.
  • vapour passes from the exterior to the interior of the porous hollow support members 12 where it is picked up by the air flowing through the interior of the porous hollow support members 12 and passes into a heat exchanger 6. Heat is removed from the vapour by heat exchanger 6 resulting in water vapour condensing in a collecting vessel 9.
  • a vacuum pump 7 assists the passage of the vapour through heat exchanger 6 and draws the ammonium therethrough and passes it to a vessel 10 which contains warm water. The ammonium dissolves in the warm water to form ammonium hydroxide.
  • the ammonium acetate from which the ammonium hydroxide has been removed exits from the module 5 at B and is discharged from the system at reference 18.
  • References 1, 2, 3 and 4 respectively indicate a valve, a temperature gauge, a pressure gauge and a fluorometer. Using the method described above the following recovery rates may be obtained:
  • a membrane was formed on porous hollow support members contained in a membrane module manufactured by Romicon (U.S.).
  • the support members and module had the following properties:
  • hollow fibers polysulfone pore size of hollow fibers 0.02 microns diameter of hollow fibers 200 microns diameter of module 5.08 cm number of hollow fibers in module 4 effective length of module 30.48 cm
  • a membrane integrally associated with the hollow fibers was prepared by subjecting the module containing the polysulfone hollow fibers to a solution having the following composition:
  • the above solution was passed through and about and in contact with the hollow fibers in the module at a pressure of about 1 kg per cm 2 and a flow rate of about 10 cm per second.
  • the solution was cycled from the interior to exterior and/or exterior to interior of the hollow fibers for a total time of about 30 minutes.
  • the hollow fibers with the membrane were dried at 90°C at a pressure of -660 mm Hg for approximately 12 minutes.
  • a feed solution was then passed across the exterior surfaces of the hollow fibers with the membrane.
  • the feed solution was formulated to simulate a typical industrial solution and contained the following ingredients:
  • the above solution had a pH of 9.9 and was maintained at 75°C.
  • the solution was pumped into the module to flow across the exterior surfaces of the membrane coated hollow fibers. Cool air at approximately 21°C was passed through the interior of the hollow fibers.
  • the permeate passing through the membrane was condensed and frozen at below -2°C.
  • the permeate was collected for 1 hour and an analysis of the permeate solution showed that it contained the following composition:
  • the pH of the resulting solution was 10.7. This example indicates that the system can separate NH 4 CH 3 COO and recover NH 3 .
  • Example 2 A commercial nylon hollow fiber module made by Micron Separations Inc. (U.S.) was used for this example.
  • the module had the following properties:
  • a membrane integrally associated with the hollow fibers was prepared by subjecting the module containing hollow fibers to a solution having the following composition:
  • the membrane was formed as described above in Example 1 and subsequent to membrane formation the hollow fibers with the membrane were dried at 110°C.
  • the separation ability of the module was tested using a feed solution having the following composition:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention se rapporte à un élément de séparation destiné à être utilisé pour la séparation d'acétate d'ammonium et d'hydroxyde d'ammonium à partir d'un liquide contenant ces mêmes composés. L'élément de séparation comprend un élément de support creux poreux et une membrane associée solidairement à l'élément de support. On forme la membrane en soumettant l'élément de support à une solution contenant une quantité efficace d'un polysiloxane et d'un silane et, si nécessaire, un agent de réticulation pendant une période suffisamment longue pour permettre la formation d'une membrane capable de séparer l'hydroxyde d'ammonium et l'acétate d'ammonium. Un procédé est également décrit pour séparer l'acétate d'ammonium de l'hydroxyde d'ammonium au moyen de l'élément de séparation. Ledit procédé consiste à faire couler à travers et autour de l'élément de support creux poreux et en contact avec cet élément de support creux poreux une solution aqueuse contenant de l'hydroxyde d'ammonium et de l'acétate d'ammonium, puis à faire passer de l'air à travers l'intérieur de l'élément de support. La température de l'air est régulée de sorte que la différence thermique entre l'intérieur et l'extérieur de l'élément de support creux poreux soit telle que les vapeurs d'eau et d'ammonium puissent passer de l'extérieur de l'élément de support vers l'intérieur de l'élément de support. La vapeur d'eau est condensée et la vapeur d'ammonium est convertie en hydroxyde d'ammonium. Un procédé permettant la préparation de l' élément de séparation et un module de membrane contenant un ou plusieurs modules de séparation sont en outre décrits.
PCT/CA1990/000089 1989-03-18 1990-03-16 Separation d'acetate d'ammonium et d'hydroxyde d'ammonium au moyen d'une membrane Ceased WO1990011119A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU53356/90A AU5335690A (en) 1989-03-18 1990-03-16 Membrane separation of ammonium acetate and ammonium hydroxide

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN89101658.9A CN1045770A (zh) 1989-03-18 1989-03-18 用膜法蒸馏技术分离浓缩醋酸铵与氢氧化铵的系统
EP89101658.9 1989-03-18

Publications (2)

Publication Number Publication Date
WO1990011119A2 true WO1990011119A2 (fr) 1990-10-04
WO1990011119A3 WO1990011119A3 (fr) 1990-11-15

Family

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PCT/CA1990/000089 Ceased WO1990011119A2 (fr) 1989-03-18 1990-03-16 Separation d'acetate d'ammonium et d'hydroxyde d'ammonium au moyen d'une membrane

Country Status (2)

Country Link
CN (1) CN1045770A (fr)
WO (1) WO1990011119A2 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511839A3 (en) * 1991-04-29 1993-01-07 Texaco Development Corporation Membrane process for treating a mixture containing dewaxed oil and dewaxing solvent
US5472613A (en) * 1993-04-19 1995-12-05 Envirosep Inc. Removing volatile and non-volatile organic in a thick film equilibrium process and device
US6129830A (en) * 1996-12-13 2000-10-10 Atotech Deutschland Gmbh Process for the electrolytic deposition of copper layers
WO2013124190A1 (fr) * 2012-02-23 2013-08-29 Wacker Chemie Ag Procédé de traitement d'eau par distillation transmembranaire à l'aide d'une membrane en copolymème de siloxane

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102107120A (zh) * 2009-12-23 2011-06-29 天津工业大学 一种气扫式膜蒸馏方法
CN103112871B (zh) * 2013-02-19 2014-10-29 厦门国麟科技有限公司 低浓度氨水分离提纯制备高浓氨的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5973005A (ja) * 1982-09-16 1984-04-25 モンサント・コンパニ− ガス分離用多成分膜

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0511839A3 (en) * 1991-04-29 1993-01-07 Texaco Development Corporation Membrane process for treating a mixture containing dewaxed oil and dewaxing solvent
US5472613A (en) * 1993-04-19 1995-12-05 Envirosep Inc. Removing volatile and non-volatile organic in a thick film equilibrium process and device
US6129830A (en) * 1996-12-13 2000-10-10 Atotech Deutschland Gmbh Process for the electrolytic deposition of copper layers
WO2013124190A1 (fr) * 2012-02-23 2013-08-29 Wacker Chemie Ag Procédé de traitement d'eau par distillation transmembranaire à l'aide d'une membrane en copolymème de siloxane

Also Published As

Publication number Publication date
CN1045770A (zh) 1990-10-03
WO1990011119A3 (fr) 1990-11-15

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