CN101792124B - Method for producing hydrogen chloride and sodium hydrogen sulfate crystals by taking rock salt as raw material - Google Patents

Method for producing hydrogen chloride and sodium hydrogen sulfate crystals by taking rock salt as raw material Download PDF

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CN101792124B
CN101792124B CN2010190260648A CN201019026064A CN101792124B CN 101792124 B CN101792124 B CN 101792124B CN 2010190260648 A CN2010190260648 A CN 2010190260648A CN 201019026064 A CN201019026064 A CN 201019026064A CN 101792124 B CN101792124 B CN 101792124B
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sodium
sulfuric acid
rock salt
raw material
pyrosulfate
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CN101792124A (en
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褚效中
张维光
吕金顺
赵宜江
徐继明
苏娟
周守勇
李梅生
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Jiangsu Yinzhu Chemical Group Co., Ltd.
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Huaiyin Normal University
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Abstract

The invention discloses a method for producing hydrogen chloride and sodium hydrogen sulfate crystals by taking rock salt as the raw material, which comprises the following steps that: the mixture of sodium sulfate and sodium chloride, i.e. rock salt and sulfuric acid react to produce the hydrogen chloride and sodium hydrogen sulfate crystals; first, under a stirring condition, according to a certain stoichiometric ratio, sulfuric acid and rock salt are intermittently added into a glass lining reaction vessel to react while the temperature is insulated; and then sodium bisulfate solution which contains sulfuric acid is introduced to a crystal tower which contains an appropriate amount of water from the bottom of the reaction vessel to be cooled, crystallized and vacuum filter step by step, and then is washed by saturated sodium bisulfate solution to prepare sodium bisulfate crystals; and finally, the high-concentration sulfuric acid is added into the filtrate to be mixed to be sulfuric acid with the initial reaction concentration, and recycled. The method of the invention not only makes full use of natural resources, but also improves the added value of the rock salt, does not discharge any waste liquid, and meets the requirements of sustainable development.

Description

With rock salt is raw material production hydrogenchloride and sodium pyrosulfate crystalline method
Technical field
The present invention relates to the working method of hydrogenchloride and hydrosulfate, being specifically related to rock salt is raw material production hydrogenchloride and sodium pyrosulfate crystalline method.
Background technology
Hydrogen chloride gas is a kind of important chemical material, growing along with science and technology, and fine chemistry industry industries such as dyestuff, chloromethyl ether, Piperazine anhydrous, Gelucystine and agricultural chemicals, medicine intermediate and chlorinated polymer are increasing to the demand of hydrogenchloride.There is depleted low-concentration hcl behind a large amount of pickling steel in the iron and steel enterprise, therefore, can comes enrichment, make the recycle of depleted low-concentration hcl, thereby reduce the production cost of steel enterprise and the expense of environmental improvement with low-concentration hcl absorbing hydrogen chloride gas.In addition, sodium pyrosulfate is a kind of important chemical industry of inorganic salt raw material and inorganic salt solid acid catalyst, in organic syntheses such as medicine, ester compound, has a wide range of applications.
At present, though prepare the method for hydrosulfate and hydrogenchloride concentrated acid pyroprocess, diluted acid cold method (" chemical engineer " the 23rd volume the 5th phase P are arranged 22) and the concentrated acid cold method (Chinese patent: CN1188071A), but they all are to be raw material with the muriate.The concentrated acid pyroprocess is that the vitriol oil and Repone K are added in the pyroreaction still (250 ℃); On the fusing point of hydrosulfate, remove hydrogenchloride; Reacted product is solidifying below 90 ℃; Only as ammonium-potassium phosphate fertilizer midbody, and the hydrogenchloride of by-product is the high temperature corrosion gas that contains dust after being dissolved in water, and after-treatment device is complicated.The diluted acid cold method is about 120 ℃, to carry hydrogenchloride with water vapor gas with the dilute sulphuric acid of 60-75% and muriate, generates the hydrosulfate aqueous solution that contains excess sulfuric acid, and it is compared with pyroprocess; Service temperature is low, and investment relatively economizes, still; Reaction times is grown (2-5h), and energy consumption is still higher, and the hydrosulfate aqueous solution that generates is because strength of solution is rarer; Chlorinity is higher, therefore, and for reaching the chlorinity requirement of direct use; Certainly will feed a large amount of steam in the reaction later stage and deviate from residual hydrogenchloride, thereby increase cost.The concentrated acid cold method is in reaction kettle, to prepare the phase transition dispersion medium aqueous solution of excess sulfuric acid and corresponding hydrosulfate composition, under agitation condition, the muriate that measures is joined in the reaction kettle; Heat temperature raising is to boiling, in reaction kettle, progressively adds the sulfuric acid with the muriate equivalent again, treat that sulfuric acid adds after; Be incubated 30-35 minute; Be cooled to normal temperature again, the filtering for crystallizing hydrosulfate obtains finished product hydrosulfate, mother liquid recycling through washing; Though this method more preceding two class methods of operability aborning strengthens to some extent, has following problem: charging and operation process are comparatively complicated; Use water washing hydrosulfate product in this method, cause the product solution loss, and the salt behind press filtration or the suction filtration hardens easily and suction, be unfavorable for shifting and packing.
China has abundant rock salt resource, and like Huaian salt basin and Hongze lake salt basin, to the end of the year 2002, two salt basins accumulative total is verified stock number and is about 32.9 hundred million tons of (" Jiangsu geology " the 29th volume the 2nd phase P 116).The staple of rock salt is a sodium-chlor, and rock salt obtains the mixture of sodium-chlor and sodium sulfate after measure removal of impurities such as peroxo-, adding sodium hydrogencarbonate and the filtration of adjusting bittern pH value, and further separation can obtain sodium-chlor and saltcake product again.But, be the key of abundant realization " salt economy " to exploitation how low value-added Salt Production with high added value associated salts Chemicals.Developing the high-end product of rock salt simultaneously, realize that the scientific development of rock salt resource utilizes with efficient, meet the industry and the technical policy of country and local government, also is to promote the inevitable requirement that the local resources advantage is converted into the local economy advantage.
Summary of the invention
The objective of the invention is: providing a kind of is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with rock salt, and this method is that rock salt is raw material with the sodium-chlor miscellany that contains sodium sulfate, produces hydrogen chloride gas with sulfuric acid reaction; While co-producing sulfuric acid hydrogen sodium crystal; Both combine cheap rock salt characteristics of resources, made full use of the natural resources, improved the added value of rock salt again; Invest lowlyer and easy to operate, satisfy the requirement of Sustainable development.
The object of the invention is realized by following technical scheme: at first; With rock salt is that the miscellany and the sulfuric acid of sodium sulfate and sodium-chlor is raw material; Under agitation condition according to certain metering can the glassed steel reaction vessels of controlled temperature than with rock salt and sulfuric acid adding in; Open the device that absorbs or store hydrogen chloride gas simultaneously, reinforced finishing the back insulation regular hour; Then, will contain the vitriolic sodium bisulfate from reaction kettle bottom and introduce and contain the prilling tower of suitable quantity of water, the substep crystallisation by cooling, suction filtration and with the sodium bisulfate washing obtains the sodium pyrosulfate crystal; At last, filtrate and be mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, get into the reaction kettle recycle.
In the aforesaid method, described rock salt is that the quality percentage composition of sodium sulfate in sodium sulfate and the sodium-chlor miscellany is smaller or equal to 80% greater than 0.
In the aforesaid method, the sulfuric acid quality percentage composition that adds in the reaction kettle is 76-96%, preferred 80-90%.
In the aforesaid method, rock salt and vitriolic amount of substance ratio are controlled at 1: 1.7-3.5.
In the aforesaid method, said temperature of reaction is 100-160 ℃, preferred 110-130 ℃, and the reinforced back insulation 10-30min that finishes.
In the aforesaid method, prilling tower has the cooling circulating water device, and the crystallisation by cooling process was divided into for three steps: the amount of producing sodium pyrosulfate according to theory adds suitable quantity of water in prilling tower, both amount of substance ratios are 1: 0-2; At first, stirred crystallization 5-40min; Then, leave standstill crystallization 5-30min; At last, stirred crystallization 20-80min.
In the aforesaid method, said sodium bisulfate is the saturated sodium bisulfate under the Tc.
The present invention has the following advantages:
1, this method is that the miscellany of sodium sulfate and sodium-chlor is raw material production hydrogenchloride and sodium pyrosulfate crystal with rock salt; Avoided further separating of sodium-chlor and sodium sulfate; Widen the range of application of rock salt, both made full use of natural resources, improved the added value of rock salt again.
2, the reaction times shorter, production technique is simple.
3, filtrating is that chloride ion content is lower and solution that sulfuric acid concentration is higher is mixed into reaction density through high-concentration sulfuric acid to recycle easily, and the Sustainable development requirement is satisfied in no waste liquid discharge.
4, adopt Steppecd crystallization, when increasing grain-size, can prevent the generation of crystal knot tower situation, increased the flowability in the crystal transfer process.
5, the filtering and washing process is used the saturated sodium pyrosulfate aqueous solution, the solution loss of the sodium pyrosulfate that can avoid causing with water washing and caking hardening.
6, it is violent and dash the generation of material phenomenon that the existence of sodium sulfate can suppress the reaction of sodium-chlor and sulfuric acid system.
Description of drawings
A, b, c and d are respectively the sodium pyrosulfate crystalline XRD figures that analytically pure sodium sulfate, sodium-chlor, sodium pyrosulfate crystal and embodiment 5 prepare among Fig. 1.
Embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this embodiment only is used for the present invention is described further; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment according to foregoing.
Embodiment 1: add earlier the sulfuric acid of 6.00kg96% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 0.01% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 100 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 12.39kg96%, add the acid back insulation 30min that finishes; The reaction solution introducing is contained in the prilling tower of 3.82kg water, is under 5 ℃ of conditions at condensate temperature, and first stirred crystallization 5min then leaves standstill crystallization 5min, last stirred crystallization 20min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.52kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 96.98%, free acid (by sulphur acid meter) quality percentage composition is 1.98%, cl ions quality percentage composition is 0.10%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 2: add earlier the sulfuric acid of 6.00kg 90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 0.1% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 110 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 17.07kg90%, add the acid back insulation 25min that finishes; The reaction solution introducing is contained in the prilling tower of 2.86kg water, is under 10 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 10min, last stirred crystallization 35min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.55kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.56%, free acid (by sulphur acid meter) quality percentage composition is 1.93%, cl ions quality percentage composition is 0.20%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 3: add earlier the sulfuric acid of 6.00kg90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 0.5% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 120 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 22.77kg90%, add the acid back insulation 20min that finishes; The reaction solution introducing is contained in the prilling tower of 1.91kg water, is under 20 ℃ of conditions at condensate temperature, and first stirred crystallization 20min then leaves standstill crystallization 10min, last stirred crystallization 45min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.51kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.47%, free acid (by sulphur acid meter) quality percentage composition is 1.85%, cl ions quality percentage composition is 0.23%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 4: add earlier the sulfuric acid of 6.00kg90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 1% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 120 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 22.68kg90%, add the acid back insulation 20min that finishes; The reaction solution introducing is contained in the prilling tower of 1.90kg water, is under 25 ℃ of conditions at condensate temperature, and first stirred crystallization 30min then leaves standstill crystallization 10min, last stirred crystallization 50min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.57kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.51%, free acid (by sulphur acid meter) quality percentage composition is 1.90%, cl ions quality percentage composition is 0.18%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 5: add earlier the sulfuric acid of 6.00kg90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 10% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 130 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 21.15kg90%, add the acid back insulation 15min that finishes; The reaction solution introducing is contained in the prilling tower of 1.87kg water, is under 25 ℃ of conditions at condensate temperature, and first stirred crystallization 40min then leaves standstill crystallization 10min, last stirred crystallization 60min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.35kg; From XRD figure, find out, do not have sodium-chlor and sodium sulfate crystal, and sodium pyrosulfate crystalline crystal formation is better; Analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.44%, free acid (by sulphur acid meter) quality percentage composition is 1.98%, and cl ions quality percentage composition is 0.12%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 6: add earlier the sulfuric acid of 6.00kg85% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 20% sodium chloride mixture, open hydrogen chloride absorption or storage system; Under 140 ℃ of conditions of constant temperature, constantly stir, and add 85% the sulfuric acid of 26.35kg, add the acid back insulation 15min that finishes; The reaction solution introducing is contained in the prilling tower of 0.92kg water, is under 30 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 20min, last stirred crystallization 70min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 14.05kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.04%, free acid (by sulphur acid meter) quality percentage composition is 2.07%, cl ions quality percentage composition is 0.23%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 7: add earlier the sulfuric acid of 6.00kg 80% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 30% sodium chloride mixture, open hydrogen chloride absorption or storage system; Under 150 ℃ of conditions of constant temperature, constantly stir, and add 80% the sulfuric acid of 31.42kg, add the acid back insulation 20min that finishes; Reaction solution is introduced in the prilling tower, is under 35 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 25min, last stirred crystallization 80min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 13.76kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 96.86%, free acid (by sulphur acid meter) quality percentage composition is 2.42%, cl ions quality percentage composition is 0.31%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 8: add earlier the sulfuric acid of 6.00kg90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 40% sodium chloride mixture, open hydrogen chloride absorption or storage system; Under 160 ℃ of conditions of constant temperature, constantly stir, and add 90% the sulfuric acid of 16.06kg, add the acid back insulation 10min that finishes; The reaction solution introducing is contained in the prilling tower of 1.77kg water, is under 40 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 30min, last stirred crystallization 80min;
Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 13.55kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.62%, free acid (by sulphur acid meter) quality percentage composition is 1.83%, cl ions quality percentage composition is 0.16%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 9: add earlier the sulfuric acid of 6.00kg 76% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 50% sodium chloride mixture, open hydrogen chloride absorption or storage system; Under 130 ℃ of conditions of constant temperature, constantly stir, and add 76% the sulfuric acid of 24.87kg, add the acid back insulation 20min that finishes; Reaction solution being introduced crystallization in the prilling tower that contains 0.35kg water, is under 25 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 25min, last stirred crystallization 60min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 13.31kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 96.81%, free acid (by sulphur acid meter) quality percentage composition is 2.14%, cl ions quality percentage composition is 0.35%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 10: add earlier the sulfuric acid of 6.00kg 90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 60% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 120 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 11.18kg90%, add the acid back insulation 25min that finishes; The reaction solution introducing is contained in the prilling tower of 1.36kg water, is under 20 ℃ of conditions at condensate temperature, and first stirred crystallization 10min then leaves standstill crystallization 25min, last stirred crystallization 40min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 12.98kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.83%, free acid (by sulphur acid meter) quality percentage composition is 1.52%, cl ions quality percentage composition is 0.21%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 11: add earlier the sulfuric acid of 6.00kg 90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 70% sodium chloride mixture, open hydrogen chloride absorption or storage system; Under 125 ℃ of conditions of constant temperature, constantly stir, and add 90% the sulfuric acid of 13.01kg, add the acid back insulation 20min that finishes; The reaction solution introducing is contained in the prilling tower of 1.51kg water, is under 25 ℃ of conditions at condensate temperature, and first stirred crystallization 15min then leaves standstill crystallization 20min, last stirred crystallization 60min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 12.76kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.62%, free acid (by sulphur acid meter) quality percentage composition is 1.89%, cl ions quality percentage composition is 0.15%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Embodiment 12: add earlier the sulfuric acid of 6.00kg 90% at the 50L glassed steel reaction vessels that has stirring tank, TM, add 6.20kg sodium sulfate quality percentage composition again and be 80% sodium chloride mixture, open hydrogen chloride absorption or storage system simultaneously; Under 130 ℃ of conditions of constant temperature, constantly stir, and add the sulfuric acid of 9.28kg90%, add the acid back insulation 20min that finishes; The reaction solution introducing is contained in the prilling tower of 1.64kg water, is under 25 ℃ of conditions at condensate temperature, and first stirred crystallization 25min then leaves standstill crystallization 15min, last stirred crystallization 40min; Suction filtration and with saturated sodium bisulfate wash sodium pyrosulfate crystal 12.49kg, analyze wherein that sodium pyrosulfate crystal mass percentage composition is 97.45%, free acid (by sulphur acid meter) quality percentage composition is 1.95%, cl ions quality percentage composition is 0.15%; Filtrating is mixed into the sulfuric acid of initial action concentration with high-concentration sulfuric acid, gets into the reaction kettle recycle.
Among the above embodiment rock salt and vitriolic amount of substance than and prilling tower in theoretical produce sodium pyrosulfate with add water amount of substance such as following: embodiment 1: the former is 1: 1.7, and the latter is 1: 2; Embodiment 2: the former is 1: 2, and the latter is 1: 1.5; Embodiment 3: the former is 1: 2.5, and the latter is 1: 1; Embodiment 4: the former is 1: 2.5, and the latter is 1: 1; Embodiment 5: the former is 1: 2.5, and the latter is 1: 1; Embodiment 6: the former is 1: 3, and the latter is 1: 0.5;
Embodiment 7: the former is 1: 3.5, and the latter is 1: 0; Embodiment 8: the former is 1: 2.5, and the latter is 1: 1; Embodiment 9: the former is 1: 3.2, and the latter is 1: 0.2; Embodiment 10: the former is 1: 2.3, and the latter is 1: 0.8; Embodiment 11: the former is 1: 2.8, and the latter is 1: 0.9; Embodiment 12: the former is 1: 2.5, and the latter is 1: 1.

Claims (6)

1. be raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture, this method is that rock salt and sulfuric acid are raw material to contain different sodium sulfate quality fractional sodium chloride mixtures, reacted hydrogenchloride and sodium pyrosulfate crystal; It is characterized in that this method may further comprise the steps:
1. be that rock salt and sulfuric acid are raw material to contain different sodium sulfate quality fractional sodium chloride mixtures; Under agitation condition according to certain metering than sulfuric acid and rock salt are intermittently added can the glassed steel reaction vessels of controlled temperature in; Open the device that absorbs or store hydrogen chloride gas simultaneously, the reinforced end back insulation regular hour;
2. will contain the introducing of vitriolic sodium bisulfate from the reaction kettle bottom and contain the prilling tower of suitable quantity of water, the substep crystallisation by cooling, suction filtration with the sodium bisulfate washing, obtains the sodium pyrosulfate crystal;
3. high-concentration sulfuric acid is added the sulfuric acid that is mixed to initial action concentration in the filtrating, get into the reaction kettle recycle.
2. according to claim 1 is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture, it is characterized in that: the quality percentage composition of sodium sulfate is smaller or equal to 80% greater than 0 in the described rock salt.
3. according to claim 1 is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture, and it is characterized in that: vitriolic quality percentage composition is 76-96% in the described adding reaction kettle.
4. according to claim 1 is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture, and it is characterized in that: described rock salt and vitriolic amount of substance ratio are controlled at 1: 1.7-3.5.
5. according to claim 1 is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture; It is characterized in that: prilling tower has the cooling circulating water device; Described crystallisation by cooling process was divided into for three steps: the amount of producing sodium pyrosulfate according to theory adds suitable quantity of water in prilling tower, both amount of substance ratios are 1: 0-2; At first, stirred crystallization 5-40min; Then, leave standstill crystallization 5-30min; At last, stirred crystallization 20-80min.
6. according to claim 3 is raw material production hydrogenchloride and sodium pyrosulfate crystalline method with sodium-chlor and sodium sulfate mixture, and it is characterized in that: vitriolic quality percentage composition is 80-90% in the described adding reaction kettle.
CN2010190260648A 2010-02-05 2010-02-05 Method for producing hydrogen chloride and sodium hydrogen sulfate crystals by taking rock salt as raw material Expired - Fee Related CN101792124B (en)

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CN102153111B (en) * 2011-02-28 2012-07-04 绍兴市东湖生化有限公司 Method for preparing anhydrous sodium hydrogen sulfate by using ethephon production waste liquid
CN103396286B (en) * 2013-07-19 2015-09-23 淮阴师范学院 With the method that sodium-chlor and low-concentration ethanol are raw material production monochloroethane
CN106044801A (en) * 2016-05-26 2016-10-26 中国中轻国际工程有限公司 Process for producing sodium bisulfate from sodium sulfate and sodium chloride containing carrier
CN106672904A (en) * 2017-01-23 2017-05-17 科莱环境工程(北京)有限公司 Method for comprehensively treating sulfur-containing flue gas and solid waste abraum salt
CN106672903A (en) * 2017-01-23 2017-05-17 科莱环境工程(北京)有限公司 Method of recycling solid waste salts in chemical wastewater
CN106731582A (en) * 2017-01-23 2017-05-31 科莱环境工程(北京)有限公司 A kind of method of integrated treatment sulfide hydrogen acid waste gas and solid waste carnallite
CN109384198A (en) * 2018-12-13 2019-02-26 中南大学 A method of hydrochloric acid is produced with sodium chloride
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