CN102936021B - Application of calcium-chloride-containing aqueous solution in conversion exploitation of glauberite resource and conversion exploitation method of glauberite resource - Google Patents
Application of calcium-chloride-containing aqueous solution in conversion exploitation of glauberite resource and conversion exploitation method of glauberite resource Download PDFInfo
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Abstract
The invention relates to application of calcium-chloride-containing aqueous solution in conversion exploitation of a glauberite resource and a conversion exploitation method of the glauberite resource. The conversion exploitation method comprises the following steps: pouring the calcium-chloride-containing aqueous solution into a rock salt exploitation mine or a low-grade glauberite mine; dissolving and decomposing the glauberite into sparingly-soluble calcium sulfate and soluble sodium sulfate under a calcium chloride solution environment, wherein the calcium sulfate is precipitated in the mine, and the sodium sulfate is dissolved in the water; reacting all dissolved sodium sulfates react with calcium chloride in the calcium-chloride-containing aqueous solution, so as to generate the sparingly-soluble calcium sulfate, precipitate sparingly-soluble calcium sulfate in the bottom of the mine, and synchronously generate soluble sodium chloride and dissolve soluble sodium chloride in the water; and finally exploiting the mineral halide after dissolution for a period of time. According to the conversion exploitation method, the calcium-chloride-containing aqueous solution is adopted in the rock salt exploitation based on a conventional rock salt solution exploitation method, and all the associate glauberite resources in the rock salt can be exploited and utilized, so that the comprehensive utilization ratio of the rock salt resource can be increased.
Description
Technical field
The conversion exploitation method of the purposes that the aqueous solution that the present invention relates to chloride containing calcium is exploited for the conversion of glauberite resources and glauberite resources, is particularly useful for the exploitation of the rock salt (or well mine salt) containing glauberite.
Transform the method for exploitation rock salt association glauberite resources with the aqueous solution of chloride containing calcium, be exactly the mine aqueous solution of chloride containing calcium being injected rock salt specifically, while soluble salt resource such as exploitation sodium chloride, saltcake etc., utilize CaCl
2solution is conducive to the principle promoting that the molten drench of glauberite is decomposed, and makes the glauberite of association in salt mine obtain molten drench and decomposes, obtain diffluent sodium sulphate, and the SO produced after rock salt dissolving
4 2-reaction again with the Ca in solution
2+reaction forms CaSO
4precipitation, transforms simultaneously and generates available sodium chloride.Due to the existence of this reaction, solution is made to be in low nitre (sodium sulphate content is at below 12g/L) or the condition containing calcium chloride all the time, the further decomposition of glauberite can be promoted again under this condition, the whole molten drench of glauberite the most at last in rock salt is decomposed and is transformed and exploits into useful NaCl, reaches the object of the utilization rate improving rock salt mining deposits.
After deliberation, the method is also applicable to the conversion exploitation of low-grade glauberite.
Background technology
China's rock salt (with sodium chloride for main content) resource is very abundant, is distributed widely in the provinces more than ten such as Jiangsu, Jiangxi, Hunan, Hubei, Sichuan, Yunnan.With the salt (NaCl) that the underground salt mine of exploitation is produced for raw material, be collectively referred to as well mine salt, and define an industry, at present, well mine salt annual production has reached 3,800 ten thousand more than t, accounts for more than 52% of national salt total output.
The main component of rock salt is halite (i.e. NaCl), and companion's (being total to) rawore thing also common in its ore has glauberite, anhydrite, trona, sylvite, polyhalite, carnallite, celestine, thenardite, gypsum etc.Utilize rock salt from present exploitation and the ore deposit halogen composition that obtains, calcium sulfate type rock salt (economizing as representative with Sichuan etc.) and sodium sulfate type rock salt (with the province such as Jiangsu, Hunan for representative) can be roughly divided into.From the geological data analyses of various places salt mine, no matter be calcium sulfate type salt mine, or sodium sulfate type salt mine, all association glauberite, and glauberite (CaSO
4na
2sO
4) be a kind of double salt, key component is by the calcium sulfate (CaSO being slightly soluble in water
4) and sodium sulphate (Na soluble in water
2sO
4) composition, be insoluble in water.The general buried depth of rock salt resources is about next km of ground, and therefore, current rock salt mining generally all adopts solution mining method, after exploiting nearly saturated ore deposit halogen, then vacuum salt production.From theoretical and practice, cannot exploit association glauberite resources in rock salt by simple fresh water solution mining method, for now, rock salt association glauberite does not all have to be exploited utilization as mining deposits.
It is reported, to the exploitation of glauberite of high grade, main method is that traditional drought adopts method and Cavern Solution Mining method.The drought method of adopting refers to first by ore extraction be transported to ground from mineral deposit, then passes through the technological processes such as fragmentation, ball milling, close pressure, obtains nearly saturated sodium sulphate and the mixed solution containing certain calcium, magnesium ion.Cavern Solution Mining method refers to and first passes to glauberite ore bed by ground excavation tunnel, and then by the method for concentrated demolition by the avalanche of glauberite ore, the ore of avalanche is deposited in exploiting field, with the water soaking of uniform temperature, obtain the solution meeting finite concentration requirement, final acquisition has the sodium sulphate product of extensive industrial use.These two kinds of methods finally all obtain high caldo, produce sodium sulphate product, and these two kinds of method costs of winning are high, and the rate of extraction is low, and labour intensity is large, Solid state fermentation difficulty.Disclosed in CN88105819, " water dissolving exploit technology for mining glauberite " is by under fresh water Injection Well, decomposes according to the variations in temperature injecting fresh water the thick halogen that glauberite obtains contains sodium sulfate.Disclosed in CN1558086, " group-well fracture pressure steeping control aqueous fusion exploitation method of glauberite bal " and CN102191932A disclosed " Controlled solution mining method is soaked in the heat injection of glauberite original position " are for glauberite note well, dissolve and adopt the processing steps such as halogen.Therefore, adopt the pure glauberite method of the exploitation such as method or Cavern Solution Mining method by drought, obviously can not be used for the glauberite resource of exploiting rock salt association.Meanwhile, the low-grade glauberite that sodium sulphate content is on the low side, is also difficult to exploit completely and utilize by above two kinds of methods.
CN102205979A discloses the combined cycle production technology utilizing the salt of sodium sulfate type well mine salt, alkali and optional calcium product, wherein use the waste liquid produced in ammonia-soda process to replace fresh water to adopt bittern to note well, goodish effect is obtained for sodium sulfate type well mine salt.At the initial stage of the applicant after this technology being gone into operation, the annual benefit of newly-increased tens00000000, the waste liquid of a visible technique becomes the raw material of another technique, creates significant economic benefit.
Exploitation for simple glauberite has had large quantifier elimination.Qiao Yongsheng, " analysis of complex salt glauberite dissolubility ", chemical industry mineral and processing, 2nd phase in 2010, point out that based on glauberite be a kind of highly basic salt, celebrate glauberite together for Sichuan, study its rate of dissolution under aqueous slkali not of the same race and acid solution and dissolution velocity, experiment finds that the higher rate of dissolution of temperature and dissolution velocity decline rapider, glauberite is dissolved slack-off.Deng Qingyang, " the thin sight research of glauberite water-soluble procedure structure change ", mining industry research and development, the 2nd phase in 2009, point out by experiment, have studied glauberite structural thin sight change in water-soluble process.Interpretation, has drawn to draw a conclusion: the water-soluble process of glauberite had both been wrapped crystalliferous course of dissolution and also wrapped crystalliferous precipitation process.Liu Yangshu, " application of glauberite two kinds of dissolving dipping mining methods, test and qualification ", coloured mining and metallurgy, the 1st phase in 2007, have studied two kinds of solution leaching methods of glauberite.Guo Zhiqin, the dissolution kinetics of calcium sulfate " in the glauberite ", Sichuan University's journal, 1993, the factors such as temperature, rock sample granularity and mixing speed that have studied were on the impact of calcium sulfate dissolution velocity in glauberite.The apparent activation energy of being tried to achieve calcium sulfate course of dissolution in glauberite by experimental data is 50.54kJ/mol.Acquired results is determine that the dissolution conditions of glauberite and the technology of the molten calcium sulfate of exploitation resistance provide foundation.Feng Mingwu, " keeping the pre-test of glauberite Cavern Solution Mining glass gall concentration method ", chemical industry mineral and processing, point out that the maximum feature of glauberite Cavern Solution Mining production practice is the reduction of Lifting Convey amount
But, show from current data, both at home and abroad also not for the research that the exploitation of rock salt association glauberite resources utilizes, more there is no the example of industrial applications.
Summary of the invention
No matter that in sodium sulfate type or calcium sulfate type rock salt mineral reserve, generally have the glauberite of association, glauberite is insoluble in water.The solution mining method that current rock salt mining generally adopts, theory and practice proves, injects rock salt mine, can only exploit and utilize the soluble salt such as sodium chloride, sodium sulphate with fresh water, the glauberite of indissoluble then can not be utilized by exploitation, thus causes the waste of rock salt resources.
For in current rock salt mining process, the reality that association glauberite resources can not be utilized, present inventor furthers investigate repeatedly, the aqueous solution of chloride containing calcium is injected the mine of exploitation rock salt, result unexpectedly finds, the aqueous solution of chloride containing calcium promotes that in rock salt, the molten drench of association glauberite is decomposed, utilize while in rock salt, the soluble-salt such as sodium chloride, saltcake is dissolved in exploitation, rock salt association glauberite can be transformed exploitation to be used for sodium chloride, reach the object of the utilization rate improving rock salt mining deposits.In addition, according to the content of saltcake in rock salt and glauberite, control calcium ion concentration in calcium chloride solution, guarantee that in rock salt, association glauberite is all utilized by exploitation.Based on above discovery, complete the present invention.
According to a first aspect of the invention, the invention provides a kind of conversion exploitation method of glauberite resources, the method comprises: the aqueous solution of chloride containing calcium injected the mine containing glauberite resources of exploitation rock salt or inject the mine of low-grade glauberite, glauberite in ore deposit is resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, the calcium sulfate precipitation of wherein emanating is in shaft bottom, sodium sulphate then dissolves in aqueous, and dissolve the sodium sulphate and all react with the calcium chloride in the aqueous solution of chloride containing calcium, generate slightly soluble calcium sulfate and be also deposited in shaft bottom, simultaneous reactions produces solvable sodium chloride, finally, after the course of dissolution of a period of time (such as 6 hours-2 months), exploitation ore removal halogen (i.e. bittern).If calcium chloride is in shortage, low nitre ore deposit halogen will be exploited out; And when calcium chloride is excessive, the calcium chloride do not reacted is extracted along with containing the sodium chloride dissolved and the ore deposit halogen and bittern reacting the sodium chloride generated.
After the course of dissolution of a period of time, in rock salt when sodium sulphate, glauberite content meter, when inject Chlorine in Solution calcium excessive when, the calcium chloride do not reacted is extracted along with ore deposit halogen; And when injection Chlorine in Solution calcium is inexcessive, the method also can exploit out low nitre ore deposit halogen, and generally, in the ore deposit halogen of exploitation, sodium sulphate content is 0 ~ 12g/L, 1 ~ 9g/L, 2 ~ 7g/L, especially 3 ~ 5g/L.This is because: at present rock salt mining generally adopts convection type UNICOM to well, Injection Well with go out the down-hole distance of halogen well two well at about 200m, the volume in ripe salt chamber, down-hole is at 1-60 ten thousand m
3.Therefore in certain limit at the bottom of Injection Well, after under the aqueous solution Injection Well of chloride containing calcium, through rock salt dissolving, reaction, precipitation, to form chloride containing calcium and sodium chloride undersaturated ore deposit halogen, along with the flow process of ore deposit halogen, rock salt constantly dissolves, reaction, in the halogen of final ore deposit, calcium chloride will by total overall reaction, and in the halogen of ore deposit, sodium sulphate content slowly will rise from 0% simultaneously, and the rate of dissolution of glauberite can reduce along with the increase of sodium sulfate concentration.Therefore, be subject to the restriction of the molten drench resolution characteristic of glauberite, by controlling to inject Chlorine in Solution calcium content, can ensure that glauberite can all be transformed by molten drench.
The conversion exploitation method that the present invention also provides the rock salt containing glauberite resources to utilize ammonia-soda process waste liquid in addition, the method comprises the following steps:
1), utilize ammonia-soda process making from brine for alkali (Na
2cO
3), obtain solid sodium carbonate, produce waste ammonia-soda solution and ammonia alkali waste residue, wherein waste ammonia-soda solution Main Ingredients and Appearance is: CaCl simultaneously
280-130g/L, NaCl30-70g/L.
2), waste ammonia-soda solution injected under dilution or undiluted situation the mine containing glauberite resources of exploitation rock salt or inject the mine of low-grade glauberite, glauberite in ore deposit is resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, the calcium sulfate precipitation of wherein emanating is in shaft bottom, sodium sulphate then dissolves in aqueous, and dissolve the sodium sulphate and all react with the calcium chloride in the aqueous solution of chloride containing calcium, generate slightly soluble calcium sulfate and be also deposited in shaft bottom, simultaneous reactions produces solvable sodium chloride, after the course of dissolution of a period of time (such as 6 hours-2 months), exploitation ore removal halogen (i.e. bittern).If calcium chloride is in shortage, low nitre ore deposit halogen will be exploited out; And when calcium chloride is excessive, the calcium chloride do not reacted is extracted along with containing the sodium chloride dissolved and the ore deposit halogen and bittern reacting the sodium chloride generated.
Wherein, the aqueous solution of chloride containing calcium can be calcium chloride water, and such as calcium chloride concentration is 1g/L ~ 130g/L, 10 ~ 100g/L, 20 ~ 80g/L, 30 ~ 70g/L, especially 35 ~ 60g/L or 30-60g/L, particularly 40 ~ 50g/L, the most preferably calcium chloride water of 45g/L also can be also containing one or more other salt such as sodium chloride except the calcium chloride containing above-mentioned concentration, magnesium chloride, the aqueous solution of optional other impurity inevitable (this type of impurity content generally lower than 5g/L, more preferably less than 3g/L), such as it can be containing 1g/L ~ 130g/L, 10 ~ 100g/L, 20 ~ 80g/L, 30 ~ 70g/L, especially 35 ~ 60g/L, particularly 40 ~ 50g/L, most preferably about 45g/L calcium chloride and 1g/L ~ 100g/L, 10 ~ 90g/L, 20 ~ 80g/L, 20 ~ 70g/L, 20 ~ 60g/L, 20 ~ 50g/L or 30 ~ 60g/L or 30 ~ 55g/L, especially 35 ~ 50g/L, particularly 40 ~ 50g/L, the most preferably aqueous solution of about 45g/L sodium chloride, such as, contain the aqueous solution of 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium chloride, preferably contains the aqueous solution of 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium chloride.The aqueous solution of chloride containing calcium can also be the waste liquid of the chloride containing calcium produced in Chemical Manufacture, the clear calcium liquid of such as ammonia alkali (namely from ammonia alkali process containing CaCl
2waste liquid) etc. waste liquid.
Find after deliberation, in calcium chloride solution or low nitre (sodium sulphate is less than 12g/L) solution, glauberite can decompose in molten drench, and wherein calcium chloride solution is better than low nitre solution, is containing 40 ~ 50g/L, especially about 45g/L CaCl
2solution in, the dissolution velocity of glauberite is maximum, compared to the solution of calcium chloride containing other concentration, has significant improvement.
Therefore, in a preferred embodiment, the aqueous solution of above-mentioned chloride containing calcium is preferably containing 40 ~ 50g/L, the especially aqueous solution of 45g/L calcium chloride.
In another embodiment, the temperature of the aqueous solution of chloride containing calcium remains on 30 ~ 100 DEG C, preferably 35 ~ 50 DEG C, more preferably 40 ~ 50 DEG C, this is because in calcium liquid, glauberite increases along with temperature raises its dissolution velocity.As: in 40 DEG C of calcium liquid, dissolution velocity is maximum, four times of dissolution velocity when being 15 DEG C, and temperature more than 50 DEG C time, not having obvious glauberite to raise and effect that dissolution velocity increases along with temperature, is therefore uneconomic.
In a preferred embodiment, by molar amount, it is excessive for keeping the calcium chloride in the aqueous solution of chloride containing calcium to dissolve relative to down-hole the sodium sulphate during note well, thus the sodium sulphate removed completely in solution, make the solution exploiting rock salt be always the bittern (i.e. ore deposit halogen) of chloride containing calcium.
In a preferred embodiment, by molar amount, it is not enough for keeping the calcium chloride in the aqueous solution of chloride containing calcium to dissolve relative to down-hole the sodium sulphate during note well, make to exploit the bittern (i.e. ore deposit halogen) that the solution of rock salt is contains sodium sulfate (at below 12g/L), finally obtain low nitre ore deposit halogen.
In the present invention, the aqueous solution of chloride containing calcium is injected in mine and sl. sol. calcium sulfate and solvable sodium sulphate are resolved in molten for glauberite drench, the time of dissolving the slightly soluble calcium sulfate precipitation shaft bottom that the sodium sulphate that all reacts with the calcium chloride in the aqueous solution of chloride containing calcium and generates is generally 6 ~ 24 hours, preferably 10 ~ 16 hours.And actual according to the production of current rock salt mining, the solution of injection needs just can be extracted through the time in 1-February at the mine (i.e. old mine) of maturation, even if meet the new mine the most desirable also needs time of more than 2 days of exploitation.Therefore, in the present invention, calcium sulfate reaction can meet the demands completely with the sedimentation time.Therefore, in the conversion exploitation of the glauberite resources of the application, the time that course of dissolution experiences is generally 6 hours-2 months, preferably 24 hours-1.5 months, preferably 2 days-1 month further, such as 3,4,5,6,7,8,9,10,15,20,25 days.Above-mentioned time range is referred in this application as " course of dissolution of a period of time ".
According to another aspect of the present invention, the purposes that the aqueous solution providing a kind of chloride containing calcium is exploited for the conversion of glauberite resources.
According to an embodiment of this aspect, described glauberite resources is the glauberite (such as glauberite (CaSO of the association of sodium sulfate type or calcium sulfate type rock salt mineral reserve
4na
2sO
4) average content is 1-15wt%, preferred 2-10wt%, more preferably 3-8wt% or 3.5-7wt%, the especially rock salt of 4-6wt%, most preferably 4.5-5.5wt%) or low-grade glauberite." low-grade glauberite " is for purer glauberite resources in this application, and main content is glauberite, but glauberite content is relatively low, and average content is less than 20wt%, a certain amount of saltcake of symbiosis simultaneously, halite (sodium chloride) etc.The sodium sulfate in the brine content that such resource obtains is exploited also low with fresh water, obviously uneconomical as the raw material producing glauber salt with this bittern.Therefore, adopt the present invention such mining deposits can be converted into sodium chloride resource exploitation and out use, extraordinary economic worth can be produced.Such as refer to, glauberite (CaSO
4na
2sO
4) average content is less than 20wt% (such as 0-20wt% or 1-20wt%, 4-18 or 7-15wt% or 9-12wt%) and 0-12wt% (such as 1-10wt%, as 5wt%) saltcake and the glauberite of halite (sodium chloride) of 0-12wt% (such as 1-18 or 2-10wt%, as 5wt% or 7wt%).Low-grade glauberite also can contain other impurity.
According to an embodiment, the aqueous solution of chloride containing calcium is calcium chloride water, the calcium chloride water of such as 1g/L ~ 400g/L, 10 ~ 100g/L, 20 ~ 80g/L, especially 40 ~ 45g/L, particularly about 45g/L, or except also containing one or more other salt such as sodium chloride containing except calcium chloride, magnesium chloride, the aqueous solution of optional inevitable impurity, such as it can be the aqueous solution containing 1 ~ 100g/L calcium chloride and 1 ~ 100g/L sodium chloride, such as contain the aqueous solution of 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium chloride, the aqueous solution containing 30 ~ 60g/L calcium chloride and 20 ~ 50g/L sodium chloride, more preferably the aqueous solution of 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium chloride is contained, be more preferably the aqueous solution containing 40 ~ 47g/L calcium chloride (such as 45g/L calcium chloride) and 35 ~ 45g/L sodium chloride (such as 42g/L), or the waste liquid of the chloride containing calcium produced in Chemical Manufacture, the clear calcium liquid of such as ammonia alkali (namely from ammonia alkali process containing CaCl
2waste liquid) etc. waste liquid.This waste ammonia-soda solution from the high concentration in ammonia alkali technique can be used in described conversion exploitation under dilution or undiluted situation, is preferably diluted in the application for being used to after the concentration of the aqueous solution defined of chloride containing calcium in described conversion exploitation.After dilution, this waste ammonia-soda solution can be or become the aqueous solution containing 1 ~ 100g/L calcium chloride and 1 ~ 100g/L sodium chloride, such as contain the aqueous solution of 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium chloride, the aqueous solution containing 30 ~ 60g/L calcium chloride and 20 ~ 50g/L sodium chloride, more preferably contain the aqueous solution of 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium chloride, be more preferably the aqueous solution containing 40 ~ 47g/L calcium chloride (such as 45g/L calcium chloride) and 35 ~ 45g/L sodium chloride (such as 42g/L).By using the waste liquid of ammonia alkali technique, solve the difficult problem disposed waste liquid faced in Chemical Manufacture such as ammonia alkali technique.
In a preferred embodiment, when the temperature of salt mine underground mining point is slightly high such as 35 ~ 70 DEG C, more preferably 40 ~ 60 DEG C, more preferably 50 ~ 55 DEG C time, the aqueous solution of chloride containing calcium directly notes well with room temperature.When the temperature of salt mine underground mining point slightly low such as lower than 25 DEG C or lower than 20 DEG C time, the temperature of the aqueous solution of chloride containing calcium was warmed up to 30 ~ 90 DEG C, preferably 35 ~ 70 DEG C, more preferably 40 ~ 60 DEG C before note well, more preferably noted well after 50 ~ 55 DEG C.
In general, because underground rock salt component content is extremely uneven, add that subsurface geology situation is more complicated, the ore deposit halogen mass change of exploitation is large, the composition of the composition of " sodium sulfate type well mine salt " fresh water mining brine is: NaCl content is generally at 250-320g/L, preferred 270-310g/L, more preferably 280-305g/L, most preferably 290-302g/L scope (such as about 298g/L); Na
2sO
4content is generally at >12g/L-30g/L, preferred 12.5-27g/L, more preferably 17-25g/L, more preferably 19-24g/L again, most preferably 20-23g/L scope (such as about 22g/L), the general <7g/L of other impurity (comprising calcium sulfate, magnesium chloride) content, preferred <5g/L, more preferably <3g/L, more preferably <1g/L again, most preferably <0.5g/L or be even 0g/L, the application claims this kind of bittern for " high caldo ".The composition of the composition of " calcium sulfate type well mine salt " fresh water mining brine is: NaCl content generally at 250-330g/L, preferred 270-322g/L, more preferably 280-318g/L, most preferably 290-313g/L scope (such as about 310g/L); Na
2sO
4content generally at 0.5-10g/L, preferred 1.0-8g/L, more preferably 1.5-6g/L, more more preferably 1.5-4g/L, most preferably 1.6-3g/L scope (such as about 2.6g/L); CaSO
4content generally at 3-8g/L, preferred 3.5-7.2g/L, more preferably 4-6.8g/L, more more preferably 4.5-6.3g/L, most preferably 5.0-6.0g/L (such as about 5.5g/L).
But, no matter sodium sulfate type salt well ore deposit, or calcium sulfate type salt well ore deposit, often containing glauberite.When water flooding recovery, first fresh water mix with the high nitre nearly saturated ore deposit halogen existed in salt chamber, more preferential rapid solution sodium chloride and saltcake, thus make the sodium sulphate content in solution comparatively fast reach more than 12g/L, in such solution, glauberite is not easily dissolved, and thus glauberite cannot be utilized.
The application is not only particularly suitable for the high rock salt of glauberite content (i.e. well mine salt), is also suitable for low-grade glauberite, the glauberite namely containing lower glauberite content (such as, lower than 20wt%, 0.1-20wt%).Certainly, the high rock salt of glauberite content (glauberite (CaSO is most preferably applicable to
4na
2sO
4) average content is 1-15wt%, preferred 2-10wt%, more preferably 3-8wt%, especially 4-6wt%).
In the waste ammonia-soda solution that each ammonia alkali enterprise produces, composition is not identical.In the present invention, based on the soda ash output of 600,000 t/, waste ammonia-soda solution amount is generally 5-13m
3/ t soda ash (butt), more general 7-11m
3/ t soda ash, especially 8-10m
3/ t soda ash, such as about 9m
3/ t soda ash, the composition of waste ammonia-soda solution is: CaCl
2content generally at 80-130g/L (butt), preferred 90-120g/L, more preferably 95-115g/L, most preferably 100-110g/L scope (such as about 105g/L); NaCl content is generally at 30-70g/L (butt), more general 40-60g/L, especially 45-55g/L (such as about 50g/L); Ammonia alkali waste residue amount generally at 250-335kg/t soda ash (butt), more general 270-330kg/t soda ash, especially 290-325kg/t soda ash, such as about 320kg/t soda ash (butt)." t " expression " ton ".
When using above-mentioned waste ammonia-soda solution, directly can use it, or preferably, it is used after being diluted, and makes CaCl after dilution
2content is generally such as 10 ~ 100g/L, 20 ~ 80g/L, 30 ~ 70g/L, especially 35 ~ 60g/L, particularly 40 ~ 50g/L, most preferably about 45g/L.
Full content disclosed in the CN102205979A of the applicant to be introduced in the application as a reference, just as describing completely in this application.
In this application, waste ammonia-soda solution and ammonia alkali clear liquid, the clear calcium liquid of ammonia alkali are used interchangeably.Ore deposit halogen and bittern are used interchangeably.
In this application, for the aqueous solution of chloride containing calcium, simply show calcium chloride content, then the sodium chloride content of this solution is lower than 1wt% or 0-1wt%, and such as, lower than 0.5wt%, other impurity content is 0-2wt%, as 1wt%.If give calcium chloride content and sodium chloride content simultaneously, then can contain other impurity of a small amount of (such as 0-2wt%, as 1wt%).
Preferably, in this application, the aqueous solution of chloride containing calcium obtained from the waste ammonia-soda solution in ammonia alkali technique or by the waste ammonia-soda solution in ammonia alkali technique through dilution.
Effect of the present invention:
According to the present invention, the mode of halogen can be adopted with the fresh water note well in existing rock salt resources ore deposit, fresh water is replaced to exploit with the aqueous solution of chloride containing calcium, while resource such as soluble-salt such as exploitation sodium chloride, saltcake etc., in rock salt, the glauberite of association indissoluble is also converted to solvable NaCl, and obtain exploitation utilization, thus successfully broken the present situation that association glauberite can not exploit utilization, achieve the object of the utilization rate improving rock salt resources.
The advantage that the present invention has:
1, on the basis of existing solution mining rock salt method, the aqueous solution of chloride containing calcium is used in rock salt mining, association glauberite resource full extraction in rock salt can be utilized, improve the comprehensive utilization ratio of rock salt resources, solve the technical barrier that in rock salt, association glauberite resource is not utilized.
2, the aqueous solution of chloride containing calcium can be the waste liquid (need guarantee not produce rock salt resources to pollute) producing chloride containing calcium in Chemical Manufacture, the clear calcium liquid of such as ammonia alkali (such as from ammonia alkali process containing CaCl
2waste liquid) etc. waste liquid, for chemical industry waste recovery recycling has searched out an outlet, refuse is become the raw material of other industries, environment protection significance is obvious, brings significant economic benefit simultaneously.
3, the applicant is at the initial stage carrying out an invention CN102205979A, and the annual benefit of newly-increased tens00000000, along with expansion scale and production capacity, economic benefit is more remarkable.Therefore, the application has reason to believe, the following invention implemented on a large scale in the application, also can create significant economic benefit.
Accompanying drawing illustrates:
Fig. 1 shows process flow diagram of the present invention, and it comprises the aqueous solution preparing chloride containing calcium; Note well; Dissolve (glauberite is dissolved as sl. sol. calcium sulfate and solvable sodium sulphate), reaction (calcium chloride dissolved in the aqueous solution of sodium sulphate and the chloride containing calcium reacts), sedimentation (reacting the calcium sulfate sedimentation generated); Brine mining; Finally obtain required bittern.
Detailed description of the invention
Below further illustrate the present invention.
In the method for the invention, for rock salt mine, the aqueous solution of chloride containing calcium is injected the mine of exploitation rock salt, first, while the soluble-salt such as sodium chloride, saltcake is dissolved, in rock salt, association is also decomposed by molten drench, and obtains soluble sodium sulphate.Secondly, the calcium chloride generation chemical reaction itself contained in sodium sulphate in the solution and solution is dissolved, generation CaSO
4precipitation and solvable NaCl, CaSO
4bottom natural subsidence to mine, the sodium chloride that reaction generates then also is exploited out together along with ore deposit halogen, then is used.Meanwhile, by the reaction of excessive calcium chloride and sodium sulphate, eliminate the sodium sulphate in solution, make the solution exploiting rock salt be chloride-calcium type bittern; Or pass through the reaction of inexcessive calcium chloride and sodium sulphate, remove the part of sulfuric acid sodium in solution, the solution exploiting rock salt is made to be low nitre (sodium sulphate content is less than 12g/L) bittern, such solution environmental facilitates again the molten drench of glauberite and decomposes, thus guarantees that in rock salt, glauberite is all converted exploitation.
In the method for the invention, in conjunction with the diffusion of physical and chemical principle, principles of hydrodynamics and material and quality transfer law, glauberite corrosion process in the aqueous solution (hereinafter referred to as calcium liquid) of chloride containing calcium can be roughly divided into 3 stages.
(1) glauberite (CaSO
4na
2sO
4) meet water-soluble drench decomposition, go out Na in the molten drench of its surface contact layer
+, SO
4 2-and the Ca of trace
2+, just started to dissolve, glauberite dissolution velocity is fast, the Na gathered around glauberite
2sO
4concentration raises gradually.
(2) by diffusion, glauberite drench goes out Na
+, SO
4 2-and the Ca of trace
2+quality transmission is carried out, by high concentration to low ion concns block transitive in calcium liquid.
(3) conversion reaction, the SO that the molten drench of glauberite goes out
4 2-and the Ca of trace
2+while quality is transmitted, by the Ca contained with calcium liquid Central Plains
2+sl. sol. crystalline hydrate CaSO is generated under hydration
42H
2o; And molten drench goes out Na
+with Cl in calcium liquid
-generate NaCl.Now, at glauberite surface and a large amount of solution pervasion passage of inner formation, volume expansion, glauberite is broken also to be peeled off, and forms new interface and contacts with calcium liquid, and increase and calcium liquid contact area, facilitate the dissolving of glauberite.
Because rock salt mining is a dynamic continuous process, sodium chloride nearly saturated ore deposit halogen (i.e. nearly saturated bittern) is constantly extracted, and undersaturated calcium chloride solution is constantly supplemented, under making glauberite be in calcium chloride solution environment all the time, glauberite is molten drench constantly, thus all glauberite is all converted exploitation out.
Embodiment:
Illustrate:
(1) the rock salt component of various places is different, and content is different, and therefore, herein in embodiment, sodium sulfate type rock salt composition is for certain domestic salt mine: NaCl average content for 52.86%, Associated Constituents saltcake (Na
2sO
410H
2o) average content be 5.46%, glauberite (CaSO
4na
2sO
4) average content is 4.52%.Calcium sulfate type rock salt composition is for certain domestic salt mine: NaCl average content for 58.46%, Associated Constituents gypsum (CaSO
42H
2o) average content be 6.93%, glauberite (CaSO
4na
2sO
4) average content is 5.52%.
(2) the rock salt composition in general same place, content are extremely uneven, add that subsurface geology situation is more complicated, in embodiment, assuming that each component of rock salt mixes.
(3) calcium chloride solution can be the aqueous solution containing a certain amount of calcium chloride, with CaCl
220g/L, 40g/L or 80g/L solution is example; Also can be the aqueous solution containing a certain amount of calcium chloride and sodium chloride, to contain CaCl
2the solution of 40g/L (or 50g/L) and NaCl 40g/L is example.
(4) production-injection ratio gets 0.9, and the ore deposit halogen total salt content of exploitation is in 320g/L.
(5), during practical application, according to the actual conditions of each mine, on the basis of theory calculate, should be revised by industrial experimentation, then production application.
Embodiment 1: by 1m
3containing CaCl
2for the solution (or aqueous solution) of 20g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in water (water contained by ie in solution), simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, at the bottom of sedimentation, produce solvable sodium chloride simultaneously, be dissolved in the water, along with bittern flowing, a small amount of saltcake is also had to dissolve.After enough time sedimentation in 1 month, exploit out about 0.9m
3naCl 316g/L, Na
2sO
4low nitre ore deposit halogen (i.e. bittern) of 4g/L.
Embodiment 2: by 1m
3containing CaCl
2solution for 40g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After enough time sedimentation in 1 month, exploit out about 0.9m
3naCl 302g/L, CaCl
2the ore deposit halogen of 18g/L.
Embodiment 3: by 1m
3containing CaCl
2solution for 80g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After enough time sedimentation in 1 month, exploit out about 0.9m
3naCl 259g/L, CaCl
2the ore deposit halogen of 61g/L.
Embodiment 4: by 1m
3containing CaCl
250g/L, the solution (waste liquid from ammonia alkali production technology) of NaCl 40g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After enough time sedimentation in 1 month, exploit out about 0.9m
3naCl 299g/L, CaCl
2the ore deposit halogen of 21g/L.
Embodiment 5: by 1m
3containing CaCl
2solution for 40g/L injects calcium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After enough time sedimentation in 1 month, exploit out about 0.9m
3naCl 295.5g/L, CaCl
2the ore deposit halogen of 24.5g/L.
Embodiment 6: by 1m
3containing CaCl
2solution for 80g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After the enough time sedimentation of 1 month, exploit out about 0.9m
3naCl 259g/L, CaCl
2the ore deposit halogen of 61g/L.
Embodiment 7: by 1m
3containing CaCl
240g/L, the solution of NaCl 40g/L injects sodium sulfate type rock salt mine, rock salt is about 50 DEG C environment in down-hole, the soluble salt such as sodium chloride and saltcake is first dissolved in the water, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in down-hole, sodium sulphate is then dissolved in water, now, dissolve the sodium sulphate all to react with original calcium chloride in solution, generate slightly soluble calcium sulfate, sedimentation is low, produce solvable sodium chloride simultaneously, be dissolved in the water, the calcium chloride cannot reacted completely is extracted along with ore deposit halogen.After the enough time sedimentation of 1 month, exploit out about 0.9m
3naCl 294.2g/L, CaCl
2the ore deposit halogen of 25.8g/L.
Claims (13)
1. containing the conversion exploitation method of the rock salt of glauberite resources, the method comprises: the aqueous solution of chloride containing calcium injected the mine containing glauberite resources of exploitation rock salt or inject the mine of low-grade glauberite, glauberite in ore deposit is resolved into sl. sol. calcium sulfate and solvable sodium sulphate by molten drench under the environment of calcium chloride solution, the calcium sulfate precipitation of wherein emanating is in shaft bottom, sodium sulphate then dissolves in aqueous, and dissolve the sodium sulphate and all react with the calcium chloride in the aqueous solution of chloride containing calcium, generate slightly soluble calcium sulfate and be also deposited in shaft bottom, simultaneous reactions produces solvable sodium chloride, finally, after the course of dissolution of 6 hours-2 months, exploitation ore removal halogen.
2. method according to claim 1, wherein, the aqueous solution of chloride containing calcium is the calcium chloride water of calcium chloride concentration 10 ~ 100g/L, or also contains the aqueous solution of sodium chloride and/or magnesium chloride and other optional impurity except the calcium chloride containing above-mentioned concentration.
3. method according to claim 2, wherein, the aqueous solution of chloride containing calcium is the aqueous solution containing the calcium chloride of 10 ~ 100g/L and the sodium chloride of 1g/L ~ 100g/L.
4. method according to claim 2, wherein, the aqueous solution of chloride containing calcium is the aqueous solution containing 40 ~ 50g/L calcium chloride, and the temperature of this aqueous solution is 40 ~ 50 DEG C.
5. method according to claim 1, wherein glauberite resources is low-grade glauberite, and wherein the content of glauberite in salt resource is less than 20wt%.
6. method according to claim 1, wherein glauberite resources is the glauberite of the association of sodium sulfate type or calcium sulfate type rock salt mineral reserve, and wherein the content of glauberite in rock salt is 1-15wt%.
7. the method according to any one of claim 1 ~ 4, wherein, by molar amount, keep the calcium chloride in the aqueous solution of chloride containing calcium to be excessive relative to dissolving the sodium sulphate when noting well, thus the sodium sulphate dissolved in solution is removed completely by precipitation, make the solution exploiting rock salt be always chloride-calcium type bittern.
8. the method according to any one of claim 1 ~ 4, wherein the aqueous solution of chloride containing calcium obtained from the waste ammonia-soda solution in ammonia alkali technique or by the waste ammonia-soda solution in ammonia alkali technique through dilution.
9. the aqueous solution of chloride containing calcium is used for the purposes in the conversion exploitation of the rock salt containing glauberite resources.
10. purposes according to claim 9, wherein glauberite resources is low-grade glauberite, and wherein the content of glauberite in salt resource is less than 20wt%.
11. purposes according to claim 9, wherein glauberite resources is the glauberite of the association of sodium sulfate type or calcium sulfate type rock salt mineral reserve, and wherein the content of glauberite in rock salt is 1-15wt%.
12. according to the purposes in claim 9-11 described in any one, the wherein calcium chloride water of the aqueous solution of chloride containing calcium to be calcium chloride concentration be 10 ~ 100g/L, or the aqueous solution also containing sodium chloride and/or magnesium chloride and other optional impurity except the calcium chloride containing above-mentioned concentration.
13. according to the purposes in claim 9-11 described in any one, and wherein, the aqueous solution of chloride containing calcium is the aqueous solution containing 40 ~ 50g/L calcium chloride, and the temperature of this aqueous solution is 40 ~ 50 DEG C.
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| CN103641139A (en) * | 2013-12-03 | 2014-03-19 | 江苏银珠化工集团有限公司 | Underground brine denitration method for rock salt or associated minerals of rock salt |
| CN103754898B (en) * | 2014-02-17 | 2015-03-18 | 江苏井神盐化股份有限公司 | Method for preparing soda ash by converting sodium sulfate in low-grade rock salt or glauber salt ores |
| CN104533420A (en) * | 2014-12-19 | 2015-04-22 | 湖北双环科技股份有限公司 | Multistage-series well injection method for rock salt cavity |
| EP3064473A1 (en) * | 2015-03-02 | 2016-09-07 | Solvay SA | Process for manufacturing an aqueous sodium chloride solution |
| CN107348466A (en) * | 2017-06-30 | 2017-11-17 | 益盐堂（应城）健康盐制盐有限公司 | A kind of energy-saving and emission-reduction production method of edible salt |
| CN108675499A (en) * | 2018-05-30 | 2018-10-19 | 龙蟒佰利联集团股份有限公司 | A kind of method of chloride slag mashing waste water integrated treatment |
| CN112723391B (en) * | 2021-02-24 | 2022-11-18 | 彭赛军 | Process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings |
| CN113482577B (en) * | 2021-07-21 | 2023-01-17 | 江苏淮盐矿业有限公司 | Bittern purification and collection method |
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Address after: 223200 No. 18 Huaxi Road, Huaian District, Huaian City, Jiangsu Province Co-patentee after: JIANGSU SALT INDUSTRY RESEARCH INSTITUTE Co.,Ltd. Patentee after: JIANGSU SUYAN JINGSHEN Co.,Ltd. Address before: 223200 No. 18 Huaxi Road, Huaian District, Huaian City, Jiangsu Province Co-patentee before: JIANGSU SALT INDUSTRY INSTITUTE Patentee before: JIANGSU JINGSHEN SALT & CHEMICAL INDUSTRY Co.,Ltd. |
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Application publication date: 20130220 Assignee: JIANGXI JINGHAO SALT CHEMICAL CO.,LTD. Assignor: JIANGSU SUYAN JINGSHEN Co.,Ltd.|JIANGSU SALT INDUSTRY RESEARCH INSTITUTE Co.,Ltd. Contract record no.: X2023990000704 Denomination of invention: The use of aqueous solutions containing calcium chloride for the conversion and extraction of calcium sulfate resources and the conversion and extraction methods of calcium sulfate resources Granted publication date: 20150318 License type: Exclusive License Record date: 20230712 |