CN106430247A - Method for preparing high-concentration sodium hydroxide by ultrasonically intensifying sodium sulfate - Google Patents

Method for preparing high-concentration sodium hydroxide by ultrasonically intensifying sodium sulfate Download PDF

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Publication number
CN106430247A
CN106430247A CN201611073246.7A CN201611073246A CN106430247A CN 106430247 A CN106430247 A CN 106430247A CN 201611073246 A CN201611073246 A CN 201611073246A CN 106430247 A CN106430247 A CN 106430247A
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China
Prior art keywords
sodium hydroxide
reaction
concentration
sodium sulfate
sodium
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CN201611073246.7A
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Inventor
张俊丰
麻洋
符辉
曹靖
黄妍
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Xiangtan University
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Xiangtan University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04Hydroxides

Abstract

The invention discloses a method for preparing high-concentration sodium hydroxide by ultrasonically intensifying sodium sulfate. The method comprises the following steps of conversion reaction, ultrasonic causticization, oxalic acid regeneration and the like. According to the method disclosed by the invention, a product layer wrapping a reactant during a causticization alkali production process is broken down by utilizing cavitation of ultrasonic wave, surface updating is completed, and high-efficiency preparation of the high-concentration sodium hydroxide is realized; the utilization rate of raw materials is high, the reaction efficiency is high, no 'three wastes' pollution is generated, energy consumption is reduced, and the preparation method for caustic soda is economically feasible and environment-friendly and has a very good industrial application value.

Description

A kind of method that intensified by ultrasonic wave sodium sulfate prepares high-concentration sodium hydroxide
Technical field
The present invention relates to a kind of method that intensified by ultrasonic wave sodium sulfate prepares high-concentration sodium hydroxide, belong to chemical industry neck Domain is it is adaptable to the comprehensive utilization of sodium sulfate byproduct.
Background technology
Sodium sulfate is one of eight big chemical industry basic products in the world.Industrially it is widely used in weaving, papermaking, synthesis of detergent The industries such as agent, medication chemistry, are also listed in the chemical products series of large-scale industrial production in the world.Sodium sulfate in 2011 Volume of production reached 700,000 tons/year in the whole world, wherein, China just account for 450,000 tons/year.With the growth of yield, to general The demand of the sodium sulfate of granule is but declining, and in the recent period, most of enterprise has occurred as soon as unsalable phenomenon, asks for being far longer than.At present, Most of sodium sulfate enterprises also all suffer from this problem, stockpiling of unsold product in the world, and price is low, margins weak.A lot of chemical industry simultaneously Substantial amounts of sodium sulfate byproduct is had to produce with environmental conservation process, these sodium sulfate are worth not high.
Caustic soda is important basic chemical industry raw material, is widely used in light industry, chemical industry, weaving, printing and dyeing, medicine, metallurgy, oil With industries such as military projects, national economy accounts for critical role.With the monitoring increasingly stringent to environmental protection for the country, upstream is mostly Producer of area stops production, especially Shandong District, causes caustic soda production to reduce, forms the state that supply falls short of demand.Caustic soda (32%) in 2016 Go up 34% price season, half a year has gone up 55%.Caustic soda industry is very strong to the dependency of the energy, continues Promote Technology, Realize during energy-saving and emission-reduction are the constant pursuit of Caustic soda industry, " 13 ", China's Caustic soda industry will go further to intensive, The production mode reform of Caustic soda need to accelerate to develop to the direction of high benefit, energy-saving.
In sum, the technique that exploitation prepares high-concentration sodium hydroxide with sodium sulfate for raw material has great economy meaning, If enabling industrialization, offer one can be comprehensively utilized for the substantial amounts of sodium sulfate byproduct that the industries such as chemical industry, metallurgy produce The good technology path of bar.Chinese patent(CN 1085186A)Provide a kind of method that Natrii Sulfas prepare Caustic soda, its process is such as Under:
(One)The preparation of sodium bioxalate
Na2SO4+2H2C2O4→2NaHC2O4+H2SO4
By Natrii Sulfas and oxalic acid with 1:2~1:2.5 mol ratio mixes in aqueous, stirring at normal temperature 15 ~ 40 minutes, reactant liquor mistake Filter.
(Two)Causticization
(1)The preparation of Disodium oxalate.
NaHC2O4+NaOH→Na2C2O4+H2O
In order to improve causticizing reaction speed, sodium bioxalate dilute solution of sodium hydroxide is neutralized to neutrality.Now, neutral solution is Disodium oxalate..
(2)The preparation of sodium hydroxide
Ca(OH)2+Na2C2O4→CaC2O4+2NaOH
By Ca (OH)2With Na2C2O4Equimolar mixing in aqueous, reactant liquor is first heated to reflux stirring 1 ~ 2h, then again in room The lower stirring reaction 3 ~ 4h of temperature.
(3)Secondary causticization
Utilize to improve feedstock circulation, after the filter cake of upper step reaction adds water, continue reaction under the conditions of identical causticization.
(Three)The regeneration of oxalic acid
CaC2O4+H2SO4→H2C2O4+CaSO4
By calcium oxalate and dilute sulfuric acid with 1:3~1:6 mixed in molar ratio, stirred under reflux temperature reaction 1h, reacting liquor while hot sucking filtration, Filter cake is mainly CaSO4, after filtrate cooling, separate out H2C2O4Crystal.
This method can prepare the soda bath of 2.2 ~ 2.4mol/L, but has that operating process is complicated, causticization basicity is not high Etc. weak point.Course of reaction has two problems to need to pay attention to, and one is lime water Ca (OH)2Suspension and solvable Na2C2O4Instead Should, generate solid CaC2O4With solvable NaOH, the CaC of generation2O4Ca (OH) can be wrapped in2Surface, forms product layer, thus Hinder Ca (OH)2With Na2C2O4Reaction further, causticizing reaction to be made carry out thoroughly it is necessary to take enhancements in time will It is wrapped in Ca (OH)2The CaC on surface2O4Product shell is pulverized and is peeled off in time;Two is that causticizing reaction need to be heated at reflux, and technique is multiple Miscellaneous and energy consumption higher it is necessary to develop more technically reliable, an economically viable process route.
Content of the invention
In order to solve the problems, such as causticizing reaction product layer encapsulation reaction thing, hinder reaction to carry out, simplification of flowsheet simultaneously, The invention provides a kind of method that intensified by ultrasonic wave sodium sulfate prepares high-concentration sodium hydroxide.The method combines the sky of ultrasound wave Change acts on, i.e. the effect such as the high temperature of the moment generation in collapse, high pressure, the ripple that impulses using cavitation bubble, makes to float on a liquid The surface of solids be subject to destroying drastically, remove the calcium oxalate granule being wrapped in the surface of solids in time, enable causticizing reaction fast Speed is carried out, and improves the efficiency of reaction.
The technical scheme is that:
A kind of method that intensified by ultrasonic wave sodium sulfate prepares high-concentration sodium hydroxide, comprises the steps:
(One)Conversion reaction
Na2SO4+2H2C2O4→2NaHC2O4+H2SO4
By sodium sulfate and oxalic acid dihydrate with 1:The amount of 1 ~ 2.5 material, than mixed dissolution in aqueous, is stirred at room temperature anti- Answer 15 ~ 60min, NaHC2O4·H2O crystallization separates out, and by reactant liquor sucking filtration, then filter cake is dried, weighs.Filter cake main component is Sodium bioxalate hydrate, clear liquid main component is the sulphuric acid and unreacted raw material on a small quantity that reaction generates, and clear liquid can be used for processing Causticization by-product, reaches the purpose of oxalic acid regeneration.This reaction Na+Conversion ratio be about 80 ~ 90%, due to can be recycled, finally Conversion ratio is close to 100%.
(Two)Ultrasonic causticization
(1)The preparation of Disodium oxalate.
NaHC2O4+NaOH→Na2C2O4+H2O
In order to improve causticizing reaction speed, the sodium hydroxide solution of sodium bioxalate low concentration is neutralized to neutrality, now, neutral Solution is Disodium oxalate.;
(2)Ultrasonic causticizing reaction
CaO+Na2C2O4→CaC2O4+2NaOH
By calcium oxide and Disodium oxalate. with 1:The amount of 1 ~ 1.6 material mixes than in aqueous, and reactant liquor is under conditions of ultrasonic Stirring reaction 40 ~ 80min, obtains the sodium hydroxide solution that concentration is 2.0 ~ 3.7mol/L;
This step innovative point is:One is as caustic using CaO, meets water liberated heat using quick lime and carries to causticizing reaction Supply good reaction condition, reach the beneficial effect of energy-conserving and environment-protective to a certain extent;Two is the cavitation that make use of ultrasound wave Effect has carried out Surface Renewal to reactant, and the concentration of lye greatly improving reaction efficiency preparation is also apparently higher than document(CN 1085186A).
(Three)The regeneration of oxalic acid
CaC2O4+H2SO4→H2C2O4+CaSO4
By step(Two)Gained calcium oxalate and step(One)Gained dilution heat of sulfuric acid is with 1:The amount ratio of 3 ~ 6 materials(Calcium oxalate and sulfur The amount ratio of the material of acid)Mixing, stirred under reflux temperature reacts 30 ~ 90min, reacting liquor while hot sucking filtration, and filter cake is mainly CaSO4, after filtrate cooling, separate out H2C2O4Crystal, recycles;This step reaction conversion ratio is up to 100%.
Further, ultrasonic frequency is 10 ~ 40kHz, and the rotating speed of stirring is 500 ~ 700r/min.
Further, the mass fraction of dilution heat of sulfuric acid is 15 ~ 40%.
The beneficial effects of the present invention is:
(1)The present invention adopts CaO as caustic, meets water liberated heat using quick lime and provides suitably to causticizing reaction Reaction temperature, compared with prior art, while reducing industrial energy consumption, also shortens technological process, has good economic valency Value and industrial applicability;
(2)The present invention adopts the causticizing reaction that intensified by ultrasonic wave calcium oxide is reactant, on the one hand enhances causticizing reaction process The Surface Renewal of middle reaction mass avoids the parcel to reactant for the product layer as far as possible, is not on the other hand carrying out secondary causticization (Technological process is simplified)On the premise of the concentration of alkali is greatly improved.
Brief description
Fig. 1 is the process flow diagram of the present invention.
Specific embodiment
The present invention is described in detail to use embodiment below, but the invention is not limited in this.
Embodiment 1
(One)The preparation of sodium bioxalate
By 14.2gNa2SO4It is dissolved in the beaker equipped with 200ml water and stirring to being completely dissolved, add 23.46gH2C2O4, in room temperature Under, grind stirring 30min(Rotating speed is 650r/min)Sucking filtration afterwards, gained filter cake is placed in 100 DEG C of baking ovens and dries, weigh. Accurately weigh 0.15 ~ 0.20g powder concentration known permanganate titration, calculating its conversion ratio is 89.1%.
(Two)Ultrasonic causticization
The filter cake that 12.6g step one generates and 5gNaOH is taken to stir in 100ml aqueous solution to being completely dissolved, add 8.4g Calcium oxide, reactant liquor stirring reaction 60min under conditions of ultrasonic(Supersonic frequency is 20kHz, and rotating speed is 550r/min), take out Filter, is titrated with the hydrochloric acid of 2mol/L, and calculating naoh concentration is 2.8105mol/L.
(Three)Oxalic acid regenerates
9g calcium oxalate is dissolved in 100ml sulphuric acid(Mass fraction is 20%)In, after return stirring 60min, filter cake master after product sucking filtration Calcium sulfate to be.Oxalic acid crystal is separated out after filtrate cooling.Reacting liquor while hot titrates, and is measured with the potassium permanganate solution of concentration known Filtrate mesoxalic acid ion conversion rate is 100%.
Comparative example 1
Causticization(No ultrasonic)
Step(One)With embodiment 1
Take 12.6g step(One)The filter cake obtaining is stirred to being completely dissolved in 100ml aqueous solution with 5gNaOH, adds 8.4g Calcium oxide, reactant liquor is under agitation(No ultrasonic)Reaction 60min, sucking filtration, titrated with the hydrochloric acid of 2mol/L, calculated hydrogen Oxidation na concn is 1.6252mol/L.
Embodiment 2
(One)The preparation of sodium bioxalate
By 14.2gNa2SO4It is dissolved in the beaker equipped with 200ml water and stirring to being completely dissolved, add 25.2gH2C2O4, in room temperature Under, grind stirring 30min(Rotating speed is 650r/min)Sucking filtration afterwards, gained filter cake is placed in 100 DEG C of baking ovens and dries, weigh. With example 1, calculate its conversion ratio is 87.4% to titration method.
(Two)Ultrasonic causticization
The filter cake that 11.2g step one generates and 5gNaOH is taken to stir in 100ml aqueous solution to being completely dissolved, add 8.4g Calcium oxide, reactant liquor stirring reaction 60min under conditions of ultrasonic(Supersonic frequency is 20kHz, and rotating speed is 550r/min), take out Filter, is titrated with the hydrochloric acid of 2mol/L, and calculating naoh concentration is 2.5911mol/L.
(Three)Oxalic acid regenerates
9g calcium oxalate is dissolved in 100ml sulphuric acid(Mass fraction is 20%)In, after return stirring 60min, filter cake master after product sucking filtration Calcium sulfate to be.Oxalic acid crystal is separated out after filtrate cooling.Reacting liquor while hot titrates, and is measured with the potassium permanganate solution of concentration known Filtrate mesoxalic acid ion conversion rate is 100%.
Comparative example 2
Causticization(No ultrasonic)
Step(One)With embodiment 2
Take 11.2g step(One)The filter cake generating is stirred to being completely dissolved in 100ml aqueous solution with 5gNaOH, adds 8.4g Calcium oxide, reactant liquor is under agitation(No ultrasonic)Stirring reaction 60min, sucking filtration, titrated with the hydrochloric acid of 2mol/L, calculated Going out naoh concentration is 1.4137mol/L.
Can be seen that the contribution to the present invention for the ultrasound condition from the naoh concentration of above comparative example and embodiment gained Very big, the concentration extremely considerably enhancing sodium hydroxide has namely obtained significantly more sodium hydroxide.

Claims (3)

1. a kind of intensified by ultrasonic wave sodium sulfate prepares the method for high-concentration sodium hydroxide it is characterised in that comprising the steps:
(1)Conversion reaction, by sodium sulfate and oxalic acid dihydrate with 1:The amount of 1 ~ 2.5 material than mixing, be stirred at room temperature reaction 15 ~ 60min, is filtrated to get sodium bioxalate;
(2)Ultrasonic causticization, first by step(1)Gained sodium bioxalate and dilute solution of sodium hydroxide hybrid reaction, to neutral, obtain grass Acid sodium solution, then calcium oxide is pressed 1 with Disodium oxalate.:The amount of 1 ~ 1.6 material mixes than in aqueous, and gained mixed liquor is super Stirring reaction 40 ~ 80min under conditions of sound, obtains the sodium hydroxide solution that concentration is 2.0 ~ 3.7mol/L;
(3)Oxalic acid regenerates, by step(2)Gained calcium oxalate and step(1)The dilution heat of sulfuric acid obtaining is by 1:The amount ratio of 3 ~ 6 materials Mixing, stirred under reflux temperature reacts 30 ~ 90min, reacting liquor while hot sucking filtration, separates out H after filtrate cooling2C2O4Crystal.
2. intensified by ultrasonic wave sodium sulfate according to claim 1 prepare high-concentration sodium hydroxide method it is characterised in that Step(2)In, ultrasonic frequency is 10 ~ 40kHz, and the rotating speed of stirring is 500 ~ 700r/min.
3. intensified by ultrasonic wave sodium sulfate according to claim 1 prepare high-concentration sodium hydroxide method it is characterised in that Step(3)In, the mass fraction of dilution heat of sulfuric acid is 15 ~ 40%.
CN201611073246.7A 2016-11-29 2016-11-29 Method for preparing high-concentration sodium hydroxide by ultrasonically intensifying sodium sulfate Pending CN106430247A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892311A (en) * 2017-11-13 2018-04-10 龙蟒佰利联集团股份有限公司 A kind of method that waste water of sulfur acid sodium prepares sodium hydroxide
CN109694955A (en) * 2019-02-20 2019-04-30 湘潭大学 A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085186A (en) * 1993-10-14 1994-04-13 戈京国 A kind of method for preparing caustic soda by saltcake
CN101591029A (en) * 2008-05-28 2009-12-02 北京紫光英力化工技术有限公司 Causticizing process prepares the novel process of caustic soda and super fine calcium carbonate
CN101898776A (en) * 2009-05-27 2010-12-01 北京紫光英力化工技术有限公司 New process for co-producing ultra-fine white carbon black and calcium carbonate
CN101993096A (en) * 2009-08-13 2011-03-30 孙丰一 Method for producing caustic soda liquor with sodium sulfate decahydrate
CN102847479A (en) * 2012-10-11 2013-01-02 北京化工大学 High-capacity ultrasonic crushing and dispersing device
CN103342377A (en) * 2013-07-23 2013-10-09 山东南山铝业股份有限公司 Method for removing sodium oxalate from sodium aluminate solution through lime causticization
CN103585864A (en) * 2013-07-06 2014-02-19 蒋克旭 Flue gas cleaning method capable of simultaneously desulfurizing and denitrifying

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1085186A (en) * 1993-10-14 1994-04-13 戈京国 A kind of method for preparing caustic soda by saltcake
CN101591029A (en) * 2008-05-28 2009-12-02 北京紫光英力化工技术有限公司 Causticizing process prepares the novel process of caustic soda and super fine calcium carbonate
CN101898776A (en) * 2009-05-27 2010-12-01 北京紫光英力化工技术有限公司 New process for co-producing ultra-fine white carbon black and calcium carbonate
CN101993096A (en) * 2009-08-13 2011-03-30 孙丰一 Method for producing caustic soda liquor with sodium sulfate decahydrate
CN102847479A (en) * 2012-10-11 2013-01-02 北京化工大学 High-capacity ultrasonic crushing and dispersing device
CN103585864A (en) * 2013-07-06 2014-02-19 蒋克旭 Flue gas cleaning method capable of simultaneously desulfurizing and denitrifying
CN103342377A (en) * 2013-07-23 2013-10-09 山东南山铝业股份有限公司 Method for removing sodium oxalate from sodium aluminate solution through lime causticization

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵瑜等: "铝酸钠溶液中草酸钠的石灰苛化", 《世界有色金属》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107892311A (en) * 2017-11-13 2018-04-10 龙蟒佰利联集团股份有限公司 A kind of method that waste water of sulfur acid sodium prepares sodium hydroxide
CN109694955A (en) * 2019-02-20 2019-04-30 湘潭大学 A kind of pre- sulfur method of lead plaster based on the double alkali of sodium calcium

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