CN101844779A - Manufacturing process of coarse grained thenardite - Google Patents

Manufacturing process of coarse grained thenardite Download PDF

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Publication number
CN101844779A
CN101844779A CN 201010178868 CN201010178868A CN101844779A CN 101844779 A CN101844779 A CN 101844779A CN 201010178868 CN201010178868 CN 201010178868 CN 201010178868 A CN201010178868 A CN 201010178868A CN 101844779 A CN101844779 A CN 101844779A
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saltcake
glass gall
crystal
magma
regulation
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CN101844779B (en
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苟兴无
李春先
李洪清
张大明
刘泽民
李栋良
刘文良
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SICHUAN CHUANMEI SPEICAL GLAUBER SALT CO Ltd
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SICHUAN CHUANMEI SPEICAL GLAUBER SALT CO Ltd
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Abstract

The invention discloses a manufacturing process of coarse grained thenardite, which is characterized in that under the monitoring of a DCS automatic monitoring system and the control of AK liquid balancing flow-rate meter, raw glass gall with a given concentration which is conveyed in the well is mechanically removed foreign matters by a primary pipeline filter and is precisely purified by a four-stage ion exchanger to obtain refined glass gall with low content of foreign matter, after pH value of the refined glass gall is adjusted, the refined glass gall is inputted to a continuous crystallization process system, after continuous solid-liquid separation in a primary centrifugal, the refined glass gall is re-inputted to a multilevel screw-type vacuum dryer to be dried and dehydrated and then to be conveyed to a fluidized bed to be treated, and after mirabilite with coarse grain is separated, the coarse grained thenardite is obtained.

Description

A kind of manufacturing process of coarse grained thenardite
Affiliated technical field:
The invention belongs to the precision work field of inorganic chemical, or field of fine chemical.
Background technology:
And anhydrous sodium sulphate also claims anhydrous nitre, thenardite, Sodium sulfate anhydrous.min(99); White particulate crystallization or powder, soluble in water, water absorbability is arranged, odorless is nontoxic.
Sodium sulfate can form seven water things and ten water things, seven water thing (Na 2SO 47H 2O) be white rhomboidal crystal.Transfer anhydride when being heated to 24.4 ℃ to.Sodium sulfate and carbon are reduced to sodium sulphite when pyroreaction
Therefore, be widely used in manufacturing sodium sulphite, water glass etc. also are used for papermaking, glass, printing and dyeing, synthon, process hides, food,, technology such as chemical industry.In addition, also as the blending agent of non-ferrous metal ore, enamel, rubber, chemical fertilizer, light material, also be the catalyzer that cement, mixed argillous additive and organic chemical industry's product are synthetic and prepare.
Traditional system nitre technical process is that the glass gall thermal evaporation is concentrated, form the supersaturated solution of saltcake, adopt centrifugation to go out the saltcake crystal, then, the saltcake crystal is carried out drying make saltcake, produce like this and will produce caking after the saltcake obtain is stored certain hour, thus use the time cause a lot of inconvenience.
In China Patent No. CN:00112995.3, introduced the method for producing thenardite with cooling, hot melt process and hot melt tower thereof, mainly be to adopt the cooling glass gall, saltcake crystallization from glass gall is separated out, adopt hot melt process that the crystal water in the saltcake crystal is removed then, though the technical process of this method is shorter, but power consumption is bigger, main is to adopt GM Refrigerator Working cooling glass gall, because this method is the open technical process of adopting, simultaneously, this method can only adopt the step mode of production; Obtaining saltcake like this also can lump at last.
In China Patent No. CN200510137987.2, introduced the method for producing large grain anhydrous sodium sulfate with natural salt lake mirabilite, its is through washing nitre, change nitre, refining, sedimentation, add the sulfuric acid neutralization, obtain clear solution, with its forced evaporation, centrifuge dehydration, warm air drying is made finished product.The technical process that this method adopts is actually makes the saltcake that contains crystal water with glass gall earlier, and then removes the crystal water in the saltcake, obtains the technological process of production of macrobead thenardite at last; The saltcake that this method obtains also can lump at last.
Introduced the method for separating saltcake (sodium sulfate) with the salt brine solution freezing and crystallizing in China Patent No. CN101041444A, its at 0-10 ℃, separation, recrystallize, makes finished product through pH value adjusting, precooling, crystallization control temperature.The technical process that this method adopts is actually makes the saltcake that contains crystal water with glass gall earlier, and then removes the free-water in the saltcake, obtains containing the saltcake technological process of production of crystal water at last; Adopt this processing method manufacturing to contain its energy consumption height of saltcake of crystal water, saltcake purity is not high yet, is unfavorable for scale operation simultaneously.
In China Patent No. 97116654.4, introduce the production method that a kind of freezing and crystallizing production contains the saltcake of crystal water, its through dehalogenation, concentrate, technical process such as beach solarization, collection, removal of impurities, this method mainly adopts cooling concentration, shines the method for system, and hot day, temperature control was 18 ℃, winter-spring season is controlled at 10 ℃, its objective is that such single stage method crystallization manufacturing contains the saltcake of crystal water, but, the saltcake purity that produces like this is not high, and unfavorable factor such as the place of need gathering is big, the possibility that wants to produce per year few hundred thousand tonnes of simultaneously is very little.
In China Patent No.: the manufacture method of having introduced a kind of special mirabilite with high purity in 2008100446515, it has adopted the method for physics and chemistry to handle the glass gall that contains various impurity, with the method for refining purifying glass gall among the present invention bigger difference is arranged, in order to improve the efficient of processing, the present invention does not need to clarify glass gall, directly removes by filter mechanical impurity.Adopt flocculation agent and precipitation agent rapidly precipitation of the metallic compounds such as calcium magnesium in the glass gall and clarification to be removed simultaneously.
The objective of the invention is to study a kind of manufacturing process of coarse grained thenardite, make it can overcome the shortcoming of existing saltcake production technology, guaranteeing under the high prerequisite of product purity, has ideal unit's production capacity more, overcome in the saltcake technological process of production shortcomings such as storage facilities is too much, thereby the technological process of production is shortened.And the dry crude particle saltcake that makes can not lumpd within the time of storing 3-3.5, the saltcake that also reduces big particle shape in the saltcake exists.
Summary of the invention:
A kind of manufacturing process of coarse grained thenardite, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, the former glass gall of the finite concentration of delivered downhole is removed the smart glass gall that mechanical impurity, the refining purification process of multistage ion-exchange obtain utmost point low impurity content through the one-level line strainer, input continuous crystallization process system, carrying out continuous solid-liquid through the first-stage centrifugal machine separates, the saltcake crystal that obtains, import spiral Vacuumdrier drying again and remove moisture content, import fluidized bed processing at last, obtain coarse grained thenardite.Its concrete manufacturing process is as follows:
1, removes mechanical impurity more than the 0.05mm through the one-level line strainer the technical process pipeline of the former glass gall of under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, under mine, exporting.
2, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 1) glass gall after handling, handle heavy metal ion such as calcium, magnesium plasma and the iron removed in the glass gall, arsenic, lead, cadmium, antimony through 8 grades of ion-exchangers, make the total contents of metal ion in glass gall such as its arsenic, lead, cadmium, antimony be lower than 35-50ppm, obtain refining sodium sulphate water.
3, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 2) smart glass gall behind the refining purifying pumps into the continuous crystallization system, the cold water of smart therein glass gall and 1-3 ℃ carries out heat exchange, forms supersaturated solution---the magma that contains the 10-20% sodium sulfate crystal; Magma is from the bottom input of crystallizer, import second crystallizer again, at input the 3rd crystallizer, crystal is grown up in crystallizer to 2-3mm, thereby form the magma of 35-40%, then magma is imported the stiff device, the saturated solution clear liquid of contains sodium sulfate Returning heat-exchanger again further participates in the circulation cooling, has so just realized saltcake crystalline continuous crystallization technology.
4, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 3) obtain the magma input stiff device of 35-40%, continue to make saltcake crystal concentration in the magma mixed solution to increase therein to return mine from the top of stiff device and continue to use, the high density saltcake crystalline mixed solution input first-stage centrifugal machine dehydration that forms at the stiff device to its clear liquid of 50-80%.
5, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 4) the high density saltcake crystal mixed solution input first-stage centrifugal machine dehydration process that obtains, form the saltcake crystal that contains free water 2--3%.
6), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 5) obtain containing the saltcake crystal that free water is 0.5-1%, import three grades of spiral Vacuumdriers and carry out drying, drying temperature is controlled at 150-200 ℃, import fluidized bed processing again, obtaining water content is the dry crude particle saltcake of 0.2-0.3%
7), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 5) product that obtains do not lump within 3-3.5 through the thenardite after the fluidized bed processing.
Technology of the present invention has following characteristics:
1, it is few to stick to the saltcake crystal of inwall, crystallizer inwall, stiff device inwall of heat exchanger, has reduced clearance time, production efficiency height, energy efficient.
2, adopt AK fluid balance under meter, the volumetric flow rate of the former glass gall of regulating and controlling, refining glass gall.
3, adopt the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter to control the sodium sulfate concentration of former glass gall, and magma concentration in the crystallizer, stiff device.
4, adopt crystallizer within the very short time, to grow up to 2-3mm by the time crystal.
5, adopt crystal stiff device within the very short time, to make magma concentration bring up to 50-80%,
6, adopt the first-stage centrifugal dehydration technique, improve saltcake crystalline production capacity.
7, adopt multiple coil formula Vacuumdrier, simplified saltcake crystal dehydration process, improve the saltcake production capacity.
8, this technological process of production adopts closed circuit water circulation system, makes discharged waste water be reduced to minimum level, helps environment protection.
The present invention adopts the purpose of line strainer, reduces the former glass gall settling bowl that filters usefulness on the one hand, has also shortened technical process on the other hand, also reduces the work such as desilting of former glass gall settling bowl, has reduced production and operation cost.
Adopt ion-exchanger, make on the one hand that the various metal ion contents except that sodium ion drop to minimum in the refining sodium sulphate water, be not add the additive that heavy metal ion such as removing calcium, magnesium plasma and iron, arsenic, lead, cadmium, antimony is used on the other hand, cut operating costs, technical process simultaneously shortens to 30% of technical process in the past.
Adopt crystallizer, enhance productivity on the one hand, reduce energy consumption on the other hand.Because in the continuous crystallisation system, must make the temperature of magma mixed solution remain on 10-11 ℃, only in this way just can make saltcake crystalline concentration remain on stable status, help the crystallization of saltcake saturated liquid.
The present invention's production technique of saltcake that breaks traditions fully for this reason, adopt the manufacturing process flow of continuous crystallization saltcake, technical process such as regulator control system, filter pipeline system, ion exchange system, continuous crystallisation system and the continuously centrifuged dewatering system of the monitoring by adopting the DCS Automatic monitoring systems and the regulation and control of AK fluid balance under meter and AK fluid balance under meter, continuously spiral vacuum drying system, fluid bed processing system.Not only improve the production capacity of saltcake but also shortened the thenardite technological process of production, also improved the product purity of saltcake simultaneously, reduced production and operation cost.
Technology of the present invention, be under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, the 24-30 ° of former glass gall of Be concentration of delivered downhole to be removed the smart glass gall that mechanical impurity, the refining purification process of level Four ion-exchanger obtain utmost point low impurity content through the one-level line strainer, input continuous crystallization process system, equipment such as heat exchanger, crystallizer and stiff device are arranged in the continuous crystallization system, refining glass gall carries out heat exchange with 1-3 ℃ cold water in heat exchanger, form supersaturated solution---the magma that contains the 10-20% sodium sulfate crystal; Magma is from the bottom input of first crystallizer, import second crystallizer bottom again, in input the 3rd crystallizer bottom, crystal is grown up in crystallizer to 2-3mm, thereby form the magma of 35-40%, the saturated solution clear liquid of contains sodium sulfate Returning heat-exchanger again further participates in the circulation cooling, then the magma of 35-40% is imported the stiff device, continue to make saltcake crystal concentration in the magma mixed solution to increase therein to return mine from the top of stiff device and continue to use to its clear liquid of 50-80%, the high density saltcake crystalline mixed solution input first-stage centrifugal machine that forms at the stiff device dewaters, after the magma mixed solution of high density dewaters through the first-stage centrifugal machine, formation contains the saltcake crystal of free water 0.5-1%, import three grades of spiral Vacuumdriers, drying temperature is controlled at 150-200 ℃, through after the fluidized bed processing, input automatic packaging system packs.
Line strainer that the present invention adopts adopts the import all steel to cross filter core, filter pore laser boring, pore size is even, filter reasonable pore distribution, satisfy the mechanical impurity of removing different-grain diameter, cross this strainer flushing of filter core simply than disposable macromolecular material net filter core, candle, stainless (steel) wire that present domestic line strainer filter core adopts, consume and lack characteristics such as long service life.Ion-exchanger of the present invention is mounted on the pipeline of technical process, and 8 ion-exchangers are installed altogether, i.e. one-level cation exchanger → secondary cation exchanger → three grade cation exchanger → one-level anion exchanger.
Former glass gall is removed after the mechanical impurity through the one-level line strainer on the process pipe, input one-level cation exchanger, import the secondary cation exchanger again, import three grades of cation exchangers again, import the one-level anion exchanger again, make through handling like this that the various metal ion contents except that sodium ion drop to minimum in the refining sodium sulphate water, do not add simultaneously the additive that heavy metal ion such as removing calcium, magnesium plasma and iron, arsenic, lead, cadmium, antimony is used, reduce the quality made from extra care glass gall to bring other ions into;
The DCS system is the english abbreviation of project dispersing control system, is a kind of " mixing functions type " Controlling System of controlling the field, can realize real-time tasks such as data gathering, process control, sequential control.Why being become " mixing functions type " Controlling System, is because system is when carrying out functional design, removes to have kept powerful analog quantity processing and the loop control function of conventional DCS system, also has quick logic control function and higher system real time performance concurrently.
Description of drawings:
Accompanying drawing 1 is process flow diagram of the present invention.
Embodiment
Below technology of the present invention is described in further detail.
Embodiment 1: under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter 24 ° of former glass galls of Be concentration of delivered downhole are removed the smart glass gall that mechanical impurity, the refining purification process of level Four ion-exchanger obtain utmost point low impurity content through the one-level line strainer, input continuous crystallization process system, equipment such as heat exchanger, crystallizer and stiff device are arranged in the continuous crystallization system, refining glass gall carries out heat exchange with 1 ℃ cold water in heat exchanger, form supersaturated solution---the magma that contains 20% sodium sulfate crystal; Magma is from the bottom input of crystallizer, it is 2mm that crystal is grown up to median size in crystallizer, thereby form 35% magma, the saturated solution clear liquid of its top contains sodium sulfate from overflow port again Returning heat-exchanger further participate in circulation cooling, so just realized saltcake crystalline continuous crystallization technology, then 35% magma is imported the stiff device, continue to make the saltcake crystal concentration in the magma mixed solution to increase therein to 50%, its clear liquid returns mine to be continued to use from the top of stiff device, the high density saltcake crystalline mixed solution input first-stage centrifugal machine that forms at the stiff device dewaters, formation contains the saltcake crystal of free water below 1.0%, import three grades of spiral Vacuumdriers and carry out drying, drying temperature is controlled at 150 ℃, import fluidized bed processing again after, input automatic packaging system packs.Obtaining the saltcake crystal detects various data and sees Table 1.
Embodiment 2: under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter the former glass gall of 24Be concentration of delivered downhole is removed the smart glass gall that mechanical impurity, eight grades of refining purification process of ion-exchangers obtain utmost point low impurity content through triode road strainer, input continuous crystallization process system, equipment such as heat exchanger, crystallizer and stiff device are arranged in the continuous crystallization system, refining glass gall carries out heat exchange with 3 ℃ cold water in heat exchanger, form supersaturated solution---the magma mixed solution that contains 20% sodium sulfate crystal; Magma is from the bottom input of crystallizer, it is 3mm that crystal is grown up to median size in crystallizer, thereby form 40% magma, the saturated solution clear liquid of its top contains sodium sulfate from overflow port again Returning heat-exchanger further participate in circulation cooling, so just realized saltcake crystalline continuous crystallization technology, then 40% magma is imported the stiff device, continue to make saltcake crystal concentration in the magma mixed solution to increase therein to return mine from the top of stiff device and continue to use to 80% its clear liquid, the high density saltcake crystalline mixed solution input first-stage centrifugal machine that forms at the stiff device dewaters, formation contains the saltcake crystal of free water 0.5%, import three grades of spiral Vacuumdriers and carry out drying, drying temperature be controlled at 180 ℃ import fluidized bed processing again after, input automatic packaging system packs.Obtain saltcake crystal detection data and will see Table 1.
Embodiment 3: under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter the 24-30 ° of former glass gall of Be concentration of delivered downhole removed the smart glass gall that mechanical impurity, eight grades of refining purification process of ion-exchangers obtain utmost point low impurity content through triode road strainer, input continuous crystallization process system, equipment such as heat exchanger, crystallizer and stiff device are arranged in the continuous crystallization system, refining glass gall carries out heat exchange with 3 ℃ cold water in heat exchanger, form supersaturated solution---the magma that contains 15% sodium sulfate crystal; Magma is from the bottom input of crystallizer, it is 2.5mm that crystal is grown up to median size in crystallizer, thereby form 37% magma, the saturated solution clear liquid of its top contains sodium sulfate from overflow port again Returning heat-exchanger further participate in circulation cooling, so just realized saltcake crystalline continuous crystallization technology, then 37% magma is imported the stiff device, continue to make saltcake crystal concentration in the magma mixed solution to increase therein to return mine from the top of stiff device and continue to use to 60% its clear liquid, the high density saltcake crystalline mixed solution input first-stage centrifugal machine that forms at the stiff device dewaters, formation contains the saltcake crystal of free water 0.6%, import three grades of spiral Vacuumdriers and carry out drying, drying temperature is controlled at 200 ℃, after importing fluidized bed processing again, input automatic packaging system packs.Obtain saltcake crystal detection data and see Table 1.
Table 1

Claims (3)

1. the manufacturing process of a coarse grained thenardite, under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, the former glass gall of the finite concentration of delivered downhole is removed mechanical impurity through line strainer, the refining purification process of multistage ion-exchange obtains the smart glass gall of low metal ion foreign matter content, after regulating pH value, input continuous crystallization process system, carrying out continuous solid-liquid through the first-stage centrifugal machine separates, the saltcake crystal that obtains, after importing multiple coil formula Vacuumdrier drying again, import the fluidized-bed processor processing again, stacked non-caking dry crude particle saltcake for a long time, its concrete manufacturing process is as follows:
1), removes mechanical impurity more than the 0.05mm through the one-level line strainer the technical process pipeline of the former glass gall of under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, under mine, exporting;
2), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 1) glass gall after handling, handle heavy metal ion such as calcium, magnesium, chlorion and the iron removed in the glass gall, arsenic, lead, cadmium, antimony through multistage ion-exchanger, make its arsenic, lead, cadmium, the antimony metal ion total content 35-50pm in glass gall, thereby obtain purified saltcake water;
3), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 2) smart glass gall behind the refining purifying pumps into the continuous crystallization system, the cold water of smart therein glass gall and 1-3 ℃ carries out heat exchange, forms supersaturated solution---the magma that contains the 10-20% sodium sulfate crystal; Magma is from the bottom input of crystallizer, import second crystallizer again, the 3rd crystallizer, crystal is grown up in crystallizer to 2-3mm, thereby form the magma of 30-35%, then magma is imported the stiff device, the saturated solution clear liquid of contains sodium sulfate from overflow port again the Returning heat-exchanger cooling that further participates in circulating realize the continuous crystallization of saltcake;
4), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 3) obtain the magma input stiff device of 30-35%, continue to make the saltcake crystal concentration in the magma mixed solution to increase therein to 60-70%, its clear liquid returns mine to be continued to use from the top of stiff device, and the high density saltcake crystalline mixed solution input first-stage centrifugal machine that forms at the stiff device dewaters;
5), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 4) the high density saltcake crystal mixed solution input first-stage centrifugal machine continuously dehydrating technical process that obtains, the magma mixed solution of high density forms the crystal type saltcake that contains free water 2-3% after dewatering through the first-stage centrifugal machine;
6), under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter with 5) obtain containing the saltcake crystal that free water is 0.5-1%, import three grades of spiral Vacuumdriers and carry out drying, drying temperature is controlled at 150-200 ℃, import fluidized bed processing again, obtaining water content is the dry crude particle saltcake of 0.2-0.3%;
2. according to the manufacturing process of the described coarse grained thenardite of claim 1, it is characterized in that, the described ion-exchanger that is used for is the pipeline that is directly installed on technical process under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, have 4 grades of ion-exchangers, i.e. one-level cation exchanger → secondary cation exchanger → three grade cation exchanger → one-level anion exchanger.
3. according to the manufacturing process of the described coarse grained thenardite of claim 1, it is characterized in that, three grades of described spiral Vacuumdriers are divided into elementary drying, secondary drying, three-stage drying under the regulation and control of the monitoring of DCS Automatic monitoring systems and AK fluid balance under meter, simultaneously with vacuum system, moisture is discharged when being convenient to the saltcake drying, also with pouncing on the foam system, when being convenient to every grade of dry saltcake because of vacuumizing, the saltcake particle of taking out of with moisture, and the moisture recovery system, take saltcake recovery system and retrieval system thereof out of.
CN2010101788682A 2010-05-20 2010-05-20 Manufacturing process of coarse grained thenardite Expired - Fee Related CN101844779B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102697801A (en) * 2012-05-21 2012-10-03 四川省川眉芒硝有限责任公司 Manufacturing process of flavouring-containing medicinal mirabilite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1036936A (en) * 1988-04-18 1989-11-08 王文生 The production method of SODIUMNITRATE
CN1327949A (en) * 2000-06-08 2001-12-26 徐万清 Cool-hot fusion method for preparing anhydrous sodium sulfate and its hot-fusion tower
CN1475443A (en) * 2003-07-25 2004-02-18 内蒙古远兴天然碱股份有限公司 Method of producing neutral high quality anhydrous sodium sulfate using natucal salt lake sodium sulfate decahydrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1036936A (en) * 1988-04-18 1989-11-08 王文生 The production method of SODIUMNITRATE
CN1327949A (en) * 2000-06-08 2001-12-26 徐万清 Cool-hot fusion method for preparing anhydrous sodium sulfate and its hot-fusion tower
CN1475443A (en) * 2003-07-25 2004-02-18 内蒙古远兴天然碱股份有限公司 Method of producing neutral high quality anhydrous sodium sulfate using natucal salt lake sodium sulfate decahydrate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102697801A (en) * 2012-05-21 2012-10-03 四川省川眉芒硝有限责任公司 Manufacturing process of flavouring-containing medicinal mirabilite
CN102697801B (en) * 2012-05-21 2013-04-03 四川省川眉芒硝有限责任公司 Manufacturing process of flavouring-containing medicinal mirabilite

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