CN105797604A - Preparation method of hydrochloric acid concentration osmosis film - Google Patents

Preparation method of hydrochloric acid concentration osmosis film Download PDF

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Publication number
CN105797604A
CN105797604A CN201610354028.4A CN201610354028A CN105797604A CN 105797604 A CN105797604 A CN 105797604A CN 201610354028 A CN201610354028 A CN 201610354028A CN 105797604 A CN105797604 A CN 105797604A
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Prior art keywords
hydrochloric acid
preparation
acid concentration
permeable membrane
thin film
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CN201610354028.4A
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Chinese (zh)
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CN105797604B (en
Inventor
王琪宇
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Zhejiang Juhua Technology Center Co Ltd
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Individual
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/66Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68Polysulfones; Polyethersulfones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane manufacture
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride

Abstract

The invention relates to a preparation method of a hydrochloric acid concentration osmosis film. The preparation method includes: modifying a polyvinylidene fluoride (PVDF) thin film by using trifluoromethyl sulfinyl chloride, methylsulfonyl fluoride, methyl pyrrolethioketone, 1-ethyl-3-methylimidazole bis(trifluoromethyl sulfonyl) imide.

Description

A kind of preparation method of hydrochloric acid concentration permeable membrane
Technical field
The present invention relates to the preparation method of a kind of film, the preparation method of a kind of hydrochloric acid concentration permeable membrane.
Background technology
One of application of membrane separation technique is to recycle spent acid spent lye.Along with modern industry (iron and steel, smelting Gold, papermaking etc.) development, production process produce mineral acid alkali liquor be also continuously increased, the extraction process of such as metallic ore In employ substantial amounts of alkaline solution, a large amount of spent lye containing metallate ion can be produced.If these spent lyes do not have It is suitable to do, and not only the useful resources in waste liquid can not get reasonably recycling, but also can cause environment and water source, biology The most serious infringement.The most how these spent acid spent lyes are carried out cost-effective process, be that there is theory significance very much Research topic with using value.
CN102285641A relates to a kind of recycling process of waste hydrochloric acid, it is characterised in that: after waste hydrochloric acid is by preheating, with preparation The good calcium chloride solution as catalyst is sufficiently mixed, and enters hydrochloric acid desorber, and the reboiler bottom hydrochloric acid desorber is made Using lower precipitation, the hydrogen chloride gas of precipitation collects after subcooler and demister, dissolved with a small amount of hydrogen chloride water again It is back to hydrochloric acid desorber continue to resolve, is then passed through flash distillation diversion cans as the calcium chloride solution of catalyst and carries out preparing profit again With.Avoid the waste of hydrogen chloride, also reduce cost of sewage disposal.
Hydrochloric acid waste water device and the method reclaiming hydrochloric acid waste water are reclaimed in CN103922529A low energy consumption.This device includes Cooling absorber 5, water stream injection pump 6, and be sequentially connected waste acid pot 1, triple effect evaporator 2,2nd effect evaporator 3, imitate hydrochloric acid Desorption tower 4, described cooling absorber 5 is connected with described 2nd effect evaporator 3, described water stream injection pump 6 and described triple effect evaporator 2 phase Even.The present invention is only passed through 0.3MPa steam, then an effect hydrochloric acid desorption tower in an effect heating chamber 42 of an effect hydrochloric acid desorption tower 4 The water vapour of the containing hydrogen chloride steamed in 4 is as the thermal source of 2nd effect evaporator 3, the water of the containing hydrogen chloride of same 2nd effect evaporator 3 Steam is again as the thermal source of three vaporizers 2.
Hydrochloric acid concentration technology of the prior art is with evaporation, distillation, and extractive distillation is main, has energy consumption high, long flow path Shortcoming, in the urgent need to new extracting and concentrating technology to improve efficiency, reduces energy consumption.Electrodialysis methods can only be by 1-5%(wt%) dilute salt Acid is concentrated to 10%(wt%) hydrochloric acid of left and right, existing diffusive dialysis method and relate to the osmosis concentration technology of film and can only be concentrated to 10%(wt%) the hydrochloric acid of left and right, it is impossible to further concentration.
Summary of the invention
Present invention aim at solving above-mentioned technical problem present in prior art, it is provided that a kind of hydrochloric acid concentration permeable membrane Preparation method.It is characterized in that preparation process includes:
By weight, by 100 parts of sulfonated polyether sulfone thin film, double 18 alkyl dimethyl ammonium chlorides of 1-5 part, 100-500 part dicarboxyl Biphenyl sulfone, 1-5 part dichloroethanes, 0.01-0.1 part 1-carboxyethyl-3-methylimidazolium nitrate, 40-80 DEG C is soaked 10-40h, Pull out and dry, obtain permeable membrane.
Described sulfonated polyether sulfone thin film is commercially available prod, the product developed such as Hangzhou Xiaoshan Jiang Cheng Chemical Co., Ltd.; Described 1-carboxyethyl-3-methylimidazolium nitrate is commercially available prod, such as the product of Chinese Academy of Sciences's Lanzhou Chemical Physics Research Institute Product.
Described dicarboxylate biphenyl sulfone, double 18 alkyl dimethyl ammonium chlorides are commercially available prod.
Due to the fact that and have employed technique scheme, have the advantages that
Sulfonated polyether sulfone thin film is through double 18 alkyl dimethyl ammonium chlorides, dicarboxylate biphenyl sulfone, 1-carboxyethyl-3-Methylimidazole. nitre The modification of hydrochlorate, is improved the permeance property of hydrochloric acid, 1-5%(wt%) dilute hydrochloric acid can be concentrated to obtain quality hundred The proportion by subtraction concentration hydrochloric acid higher than 20%.
Detailed description of the invention
Following instance only further illustrates the present invention, is not to limit the scope of protection of the invention.
Embodiment 1
In 2000L reactor, by 100Kg sulfonated polyether sulfone thin film, double 18 alkyl dimethyl ammonium chlorides of 3Kg part, the two of 300Kg Carboxyl biphenyl sulfone, 2Kg dichloroethanes, the 1-carboxyethyl-3-methylimidazolium nitrate of 0.03Kg, 74 DEG C are soaked 20h, pull out and dry in the air Dry, obtain permeable membrane.Production code member M-1.
Embodiment 2
In 2000L reactor, by 100Kg sulfonated polyether sulfone thin film, double 18 alkyl dimethyl ammonium chlorides of 1Kg, the dicarboxyl of 10Kg Biphenyl sulfone, 1Kg dichloroethanes, the 1-carboxyethyl-3-methylimidazolium nitrate of 0.01Kg, 40 DEG C are soaked 40h, pull out and dry, Obtain permeable membrane.Production code member M-2.
Embodiment 3
In 2000L reactor, by 100Kg sulfonated polyether sulfone thin film, double 18 alkyl dimethyl ammonium chlorides of 5Kg, the dicarboxyl of 500Kg Biphenyl sulfone, 5Kg dichloroethanes, the 1-carboxyethyl-3-methylimidazolium nitrate of 0.1Kg, 80 DEG C are soaked 10h, pull out and dry, To permeable membrane.Production code member M-3.
Comparative example 1 dicarboxylate biphenyl sulfone is added without, the other the same as in Example 1, production code member M-4.
Comparative example 2 1-carboxyethyl-3-methylimidazolium nitrate is added without, the other the same as in Example 1, production code member M-5.
Comparative example 3
Double 18 alkyl dimethyl ammonium chlorides are added without, the other the same as in Example 1, production code member M-6.
Comparative example 4
Use sulfonated polyether sulfone thin film as permeable membrane, production code member M-7.
Embodiment 4
Mass percent concentration be 5 hydrochloric acid put into temperature control and electromagnetic agitation the rustless steel that solvent is 2L infiltration Pond, material liquid about 400 m1. embodiment 1-3 and comparative example 1-4 prepare infiltration press mold totally 3 layers uniform in osmotic cell, Fully soaking in feed liquid and be placed in pond, on the downside of outermost tunic, pressure is maintained at 50Pa, collects through thing liquid nitrogen condensation.Adopt Analyzing material liquid and the composition of permeate by acid-base titrations, the concentration of hydrochloric acid after concentration see table:
See table:
Production code member Concentration of hydrochloric acid wt%
M-1 20
M-2 20
M-3 23
M-4 16
M-5 16
M-6 17
M-7 10
These are only the specific embodiment of the present invention, but the technical characteristic of the present invention is not limited thereto.Any with the present invention it is Basis, for solving essentially identical technical problem, it is achieved essentially identical technique effect, done simple change, equivalent are replaced Change or modification etc., be all covered by among protection scope of the present invention.

Claims (1)

1. the preparation method of a hydrochloric acid concentration permeable membrane, it is characterised in that comprise the following steps:
By weight, by 100 parts of sulfonated polyether sulfone thin film, double 18 alkyl dimethyl ammonium chlorides of 1-5 part, 100-500 part dicarboxyl Biphenyl sulfone, 1-5 part dichloroethanes, 0.01-0.1 part 1-carboxyethyl-3-methylimidazolium nitrate, 40-80 DEG C is soaked 10-40h, Pull out and dry, obtain permeable membrane.
CN201610354028.4A 2016-05-25 2016-05-25 A kind of preparation method of hydrochloric acid concentrate permeable membrane Active CN105797604B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56125205A (en) * 1980-03-06 1981-10-01 Daido Chem Eng Kk Recovering and treating method of waste hydrochloric acid
CN101898838A (en) * 2009-05-27 2010-12-01 王建刚 Method for separating iron and steel pickling waste liquid through multistage membrane dialysis
CN101979132A (en) * 2010-11-05 2011-02-23 天津森诺过滤技术有限公司 Method for preparing asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers
CN102417162A (en) * 2011-08-29 2012-04-18 浙江金壳生物化学有限公司 Recycling method of hydrochloric acid-acetic acid waste liquid
CN104291499A (en) * 2014-11-03 2015-01-21 昆山市千灯三废净化有限公司 Disposal method for iron and steel pickling waste water containing hydrochloric acids

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56125205A (en) * 1980-03-06 1981-10-01 Daido Chem Eng Kk Recovering and treating method of waste hydrochloric acid
CN101898838A (en) * 2009-05-27 2010-12-01 王建刚 Method for separating iron and steel pickling waste liquid through multistage membrane dialysis
CN101979132A (en) * 2010-11-05 2011-02-23 天津森诺过滤技术有限公司 Method for preparing asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers
CN102417162A (en) * 2011-08-29 2012-04-18 浙江金壳生物化学有限公司 Recycling method of hydrochloric acid-acetic acid waste liquid
CN104291499A (en) * 2014-11-03 2015-01-21 昆山市千灯三废净化有限公司 Disposal method for iron and steel pickling waste water containing hydrochloric acids

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