CN102936021A - 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 present invention relates to the aqueous solution of chloride containing calcium for the purposes of the conversion exploitation of glauberite resources and the conversion reoovery method of glauberite resources, be particularly useful for containing the exploitation of the rock salt (or well mine salt) of glauberite.
The aqueous solution with chloride containing calcium transforms the method for exploiting rock salt association glauberite resources, is exactly the mine that the aqueous solution of chloride containing calcium is injected rock salt specifically, in the soluble salt resources such as exploitation sodium-chlor, saltcake, utilizes CaCl
2Solution is conducive to promote the principle that the molten drench of glauberite is decomposed, and makes in the salt mine glauberite of association obtain molten drench and decomposes, and obtains diffluent sodium sulfate, and the SO that produces behind the rock salt dissolving
4 2-The reaction again with solution in Ca
2+Reaction forms CaSO
4Precipitation transforms simultaneously and generates available sodium-chlor.Because the existence of this reaction, so that solution is in all the time low nitre (sodium sulphate content is below 12g/L) or contains the condition of calcium chloride, can promote again the further decomposition of glauberite under this condition, useful NaCl is exploited in the whole molten drenches decomposition of glauberite in the rock salt and conversion the most at last, has reached the purpose that improves the utilization ratio of rock salt mining deposits.
After deliberation, the method also is applicable to the conversion exploitation of low-grade glauberite.
Background technology
China's rock salt (take sodium-chlor as main content) resource is very abundant, is distributed widely in the provinces more than ten such as Jiangsu, Jiangxi, Hunan, Hubei, Sichuan, Yunnan.Take the underground salt mine of exploitation as the salt (NaCl) of raw material production, be unified and be called well mine salt, and formed an industry, at present, the well mine salt annual production has reached more than 3,800 ten thousand t, accounts for more than 52% of national salt ultimate production.
The main component of rock salt is halite (being NaCl), in its ore also common companion's (being total to) rawore thing glauberite, anhydrite, urao, sylvite, polyhalite, carnallitite, lazurite, thenardite, gypsum etc. are arranged.Utilize rock salt and the ore deposit halogen composition that obtains from present exploitation, can roughly be divided into calcium sulfate type rock salt (take provinces such as Sichuan as representative) and sodium sulfate type rock salt (take provinces such as Jiangsu, Hunan as representative).From the geological data analyses of various places salt mine, no matter be calcium sulfate type salt mine, or the sodium sulfate type salt mine, association glauberite all, and glauberite (CaSO
4Na
2SO
4) be a kind of double salt, main ingredient is by the calcium sulfate (CaSO that is slightly soluble in water
4) and sodium sulfate (Na soluble in water
2SO
4) form, be insoluble in water.The general depth of burial of rock salt resource is about next km of ground, and therefore, at present rock salt mining generally all adopts the solution mining method, exploit nearly saturated ore deposit halogen after, vacuum salt production again.From theoretical and practice, can't exploit association glauberite resources in the rock salt with 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 that to the exploitation of glauberite of high grade, main method is that traditional drought is adopted method and Cavern Solution Mining method.The drought method of adopting refers to first then ore extraction and be transported to ground from the mineral deposit is passed through the technical process such as fragmentation, ball milling, close pressure, obtains nearly saturated sodium sulfate and contains the mixing solutions of certain calcium, magnesium ion.The Cavern Solution Mining method refers to pass to the glauberite ore bed by the ground excavation tunnel first, and then with the method for concentrated demolition with the avalanche of glauberite ore, the ore of avalanche is deposited in the exploiting field, water soaking with certain temperature, acquisition meets the solution of finite concentration requirement, the sodium sulfate product that final acquisition has extensive industrial use.These two kinds of methods finally all obtain high caldo, produce the sodium sulfate product, and these two kinds of method costs of winning are high, and the rate of extraction is low, and labour intensity is large, the waste residue difficult treatment.Be with under the fresh water Injection Well by CN88105819 disclosed " water dissolving exploit technology for mining glauberite ", decompose the thick halogen that glauberite obtains contains sodium sulfate according to the temperature variation of injecting fresh water.To annotate well, dissolve and adopt the processing step such as halogen for glauberite by CN1558086 disclosed " group-well fracture pressure steeping control aqueous fusion exploitation method of glauberite bal " and CN102191932A disclosed " heat injection of glauberite original position soak Controlled solution mining method ".Therefore, adopt the pure glauberite methods of exploitation such as method or Cavern Solution Mining method with drought, obviously can not be used for the glauberite resource of exploitation rock salt association.Meanwhile, the low-grade glauberite that sodium sulphate content is on the low side also is difficult to exploit fully and utilize with above two kinds of methods.
CN102205979A discloses the combined cycle production technology of the salt that utilizes the sodium sulfate type well mine salt, alkali and optional calcium product, wherein replacing fresh water to annotate well with the waste liquid that produces in the solvay soda process adopts bittern, has obtained goodish effect for the sodium sulfate type well mine salt.The initial stage of the applicant after this technology is gone into operation, annual newly-increased tens00000000 benefit, the waste liquid of a visible technique becomes the raw material of another technique, has produced significant economic benefit.
Exploitation for simple glauberite has had a large amount of research.Qiao Yongsheng, " analysis of composite salt glauberite solvability ", chemical industry mineral and processing, the 2nd phase in 2010, point out that based on glauberite be a kind of highly basic salt, celebrate glauberite take Sichuan together and be example, study its dissolution rate and dissolution rate under alkaline solution not of the same race and acid solution, it is rapider that experiment finds that the higher dissolution rate of temperature and dissolution rate descend, and makes the glauberite dissolving slack-off.Deng Qingyang, " the thin sight research that the water-soluble procedure structure of glauberite changes ", the mining industry research and development, the 2nd phase in 2009, point out by experiment, studied glauberite structural thin sight in water-soluble process and changed.Interpretation has drawn to draw a conclusion: the water-soluble process of glauberite had both been wrapped crystalliferous dissolution process and had also been wrapped crystalliferous precipitation process.Liu Yangshu, " application of two kinds of dissolving dipping mining methods of glauberite, test with evaluation ", coloured mining and metallurgy, has been studied two kinds of solution leaching methods of glauberite at the 1st phase in 2007.Guo Zhiqin, " dissolution kinetics of calcium sulfate in the glauberite ", Sichuan University's journal 1993, has been studied the impact of the factors such as temperature, rock sample granularity and stirring velocity on calcium sulfate dissolution rate in the glauberite.The apparent activation energy of being tried to achieve calcium sulfate dissolution process in the glauberite by experimental data is 50.54kJ/mol.Acquired results provides foundation for the dissolution conditions of determining glauberite and the technology that exploitation hinders molten calcium sulfate.Feng Mingwu, " keeping the pre-test of glauberite Cavern Solution Mining glass gall concentration method ", chemical industry mineral and processing point out that the characteristics of glauberite Cavern Solution Mining production practice maximum are to have reduced the Lifting Convey amount
But, show also not for the research of rock salt association glauberite resources exploitation utilization, more do not have the example of industrial applications both at home and abroad from present data.
Summary of the invention
No matter be in sodium sulfate type or the calcium sulfate type rock salt mineral reserve, the glauberite of association is generally arranged, glauberite is insoluble in water.The solution mining method of the at present general employing of rock salt mining, theory and practice proves, injects the rock salt mine with fresh water, can only exploit soluble salts such as utilizing sodium-chlor, sodium sulfate, the glauberite of indissoluble then can not be utilized by exploitation, thereby has caused the waste of rock salt resource.
In present rock salt mining process, the reality that the association glauberite resources can not be utilized, the present inventor furthers investigate repeatedly, the aqueous solution of chloride containing calcium is injected the mine of exploitation rock salt, the result finds beyond expectationly, the aqueous solution of chloride containing calcium promotes that the molten drench of association glauberite is decomposed in the rock salt, when exploitation utilizes in the rock salt soluble salt such as sodium-chlor, saltcake dissolved, rock salt association glauberite can be transformed exploitation and be used for sodium-chlor, reach the purpose of the utilization ratio that improves the rock salt mining deposits.In addition, according to the content of saltcake in the rock salt and glauberite, calcium ion concn in the control calcium chloride solution guarantees that the association glauberite is all utilized by exploitation in the rock salt.Based on above discovery, finished the present invention.
According to a first aspect of the invention, the invention provides a kind of conversion reoovery method of glauberite resources, the method comprises: the aqueous solution of chloride containing calcium is injected the mine that contains glauberite resources of exploiting rock salt or the mine that injects low-grade glauberite, glauberite in the ore deposit is resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, wherein the calcium sulfate precipitation of segregation is in the shaft bottom, sodium sulfate then is dissolved in the aqueous solution, and dissolve the sodium sulfate that all with the aqueous solution of chloride containing calcium in the calcium chloride reaction, generate slightly soluble calcium sulfate and also be deposited in the shaft bottom, simultaneous reactions produces soluble sodium-chlor, at last, behind the dissolution process of for some time (for example 6 hours-2 months), exploitation ore removal halogen (being bittern).If calcium chloride is in shortage, low nitre ore deposit halogen will be exploited out; And when calcium chloride was excessive, the calcium chloride that has not reacted was along with the ore deposit halogen of the sodium-chlor that the sodium-chlor that contains dissolving and reaction generate is that bittern is exploited out.
After the dissolution process of for some time, when sodium sulfate, glauberite content meter, when injecting in the excessive situation of Chlorine in Solution calcium, the calcium chloride that has not reacted is along with ore deposit halogen is exploited out in rock salt; And when injecting in the inexcessive situation of Chlorine in Solution calcium, the method also can be exploited out low nitre ore deposit halogen, and generally speaking, sodium sulphate content is 0 ~ 12g/L, 1 ~ 9g/L, 2 ~ 7g/L, especially 3 ~ 5g/L in the ore deposit halogen of exploitation.This be because: at present rock salt mining generally adopts convection type UNICOM to well, and Injection Well and the down-hole distance that goes out halogen well two wells are about 200m, and the volume in ripe salt chamber, down-hole is at 1-60 ten thousand m
3Therefore in certain limit at the bottom of the Injection Well, after under the aqueous solution Injection Well of chloride containing calcium, through rock salt dissolving, reaction, precipitation, to form the undersaturated ore deposit of chloride containing calcium and sodium-chlor halogen, along with the flow process of ore deposit halogen, rock salt constantly dissolves, reaction, calcium chloride will be by total overall reaction in the halogen of final ore deposit, and sodium sulphate content will be from 0% rising in the halogen of ore deposit simultaneously, and the dissolution rate 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, inject the Chlorine in Solution calcium contents by control, can guarantee that glauberite can be all by molten drench and conversion.
The conversion reoovery method that the present invention also provides the rock salt that contains glauberite resources to utilize ammonia-soda process waste liquid in addition, the method may further comprise the steps:
1), utilizes the solvay soda process standby alkali (Na of making from brine
2CO
3), obtain solid sodium carbonate, produce simultaneously waste ammonia-soda solution and ammonia alkali waste residue, wherein the waste ammonia-soda solution major ingredient is: CaCl
280-130g/L, NaCl30-70g/L.
2), waste ammonia-soda solution is injected the mine that contains glauberite resources of exploiting rock salt or the mine that injects low-grade glauberite in dilution or undiluted situation, glauberite in the ore deposit is resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, wherein the calcium sulfate precipitation of segregation is in the shaft bottom, sodium sulfate then is dissolved in the aqueous solution, and dissolve the sodium sulfate that all with the aqueous solution of chloride containing calcium in the calcium chloride reaction, generate slightly soluble calcium sulfate and also be deposited in the shaft bottom, simultaneous reactions produces soluble sodium-chlor, behind the dissolution process of for some time (for example 6 hours-2 months), exploitation ore removal halogen (being bittern).If calcium chloride is in shortage, low nitre ore deposit halogen will be exploited out; And when calcium chloride was excessive, the calcium chloride that has not reacted was along with the ore deposit halogen of the sodium-chlor that the sodium-chlor that contains dissolving and reaction generate is that bittern is exploited out.
Wherein, the aqueous solution of chloride containing calcium can be calcium chloride water, for example 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, 40 ~ 50g/L particularly, the calcium chloride water of 45g/L most preferably, also can be except the calcium chloride that contains above-mentioned concentration, also to contain for example sodium-chlor of one or more other salt, magnesium chloride, (this type of foreign matter content generally is lower than 5g/L to optional inevitable other impurity, more preferably less than 3g/L) the aqueous solution, for example it can be to contain 1g/L ~ 130g/L, 10 ~ 100g/L, 20 ~ 80g/L, 30 ~ 70g/L, especially 35 ~ 60g/L, 40 ~ 50g/L particularly, most preferably 45g/L left and right sides 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, 40 ~ 50g/L particularly, the aqueous solution of 45g/L left and right sides sodium-chlor most preferably, the aqueous solution that for example contains 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium-chlor preferably contains the aqueous solution of 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium-chlor.The aqueous solution of chloride containing calcium can also be the waste liquid of the chloride containing calcium that produces in the Chemical Manufacture, and for example the clear calcium liquid of ammonia alkali is (namely from the CaCl that contains in the ammonia alkali process
2Waste liquid) etc. waste liquid.
Find that after deliberation glauberite can both decompose in molten drench in calcium chloride solution or low nitre (sodium sulfate is less than 12g/L) solution, wherein calcium chloride solution is better than low nitre solution, is containing 40 ~ 50g/L, especially 45g/L left and right sides CaCl
2Solution in, the dissolution rate of glauberite is maximum, than the solution of the calcium chloride that contains other concentration, has significant improvement.
Therefore, in a preferred implementation, the aqueous solution of above-mentioned chloride containing calcium preferably contains 40 ~ 50g/L, especially the aqueous solution of 45g/L calcium chloride.
In another embodiment, the temperature of the aqueous solution of chloride containing calcium remains on 30 ~ 100 ℃, and preferred 35 ~ 50 ℃, more preferably 40 ~ 50 ℃, this is because in calcium liquid, glauberite is along with raise its dissolution rate of temperature increases.As: dissolution rate is maximum in 40 ℃ of calcium liquid, and when being 15 ℃ four of dissolution rate times, and temperature is when surpassing 50 ℃, there is not obvious glauberite to raise along with temperature and effect that dissolution rate increases, be uneconomic therefore.
In a preferred implementation, by molar weight, it is excessive that calcium chloride when annotating well in the aqueous solution of maintenance chloride containing calcium dissolves the sodium sulfate that with respect to the down-hole, thereby removes the sodium sulfate in the solution fully, so that the solution of exploitation rock salt is always the bittern (being ore deposit halogen) of chloride containing calcium.
In a preferred implementation, by molar weight, calcium chloride when annotating well in the aqueous solution of maintenance chloride containing calcium dissolves the sodium sulfate that and is deficiency with respect to the down-hole, so that the solution of exploitation rock salt is the bittern (being ore deposit halogen) of contains sodium sulfate (below 12g/L), finally obtain low nitre ore deposit halogen.
In the present invention, the aqueous solution of chloride containing calcium is injected in the mine sl. sol. calcium sulfate and soluble sodium sulfate are resolved in the molten drench of glauberite, dissolve the sodium sulfate that all with the aqueous solution of chloride containing calcium in the calcium chloride reaction and the time in the slightly soluble calcium sulfate precipitation shaft bottom that generates be generally 6 ~ 24 hours, preferred 10 ~ 16 hours.And actual according to the production of present rock salt mining, the solution of injection needs could to be exploited out through the time in 1-February at the mine (being old mine) of maturation, even satisfy the most desirable time of also needs more than 2 days of new mine of exploitation.Therefore, the calcium sulfate reaction can meet the demands fully with sedimentation time among the present invention.Therefore, in the conversion exploitation of the application's glauberite resources, the time that dissolution process experiences generally is 6 hours-2 months, preferably 24 hours-1.5 months, further preferred 2 days-1 month, for example 3,4,5,6,7,8,9,10,15,20,25 days.Refer to above-mentioned time range as for " dissolution process of for some time " in this application.
According to another aspect of the present invention, provide the purposes of a kind of aqueous solution of chloride containing calcium for the conversion exploitation of glauberite resources.
According to an embodiment of this aspect, described glauberite resources is the glauberite (glauberite (CaSO for example 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%, especially 4-6wt%, the rock salt of 4.5-5.5wt% most preferably) 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 simultaneously symbiosis, halite (sodium-chlor) etc.The sodium sulfate in the brine content that obtains with the such resource of fresh water exploitation is also low, and is obviously uneconomical as the raw material of producing Sodium sulfate anhydrous.min(99) with this bittern.Therefore, adopt the present invention such mining deposits can be converted into the sodium-chlor resource exploitation and out use, can produce extraordinary economic worth.For example refer to glauberite (CaSO
4Na
2SO
4) average content is less than 20wt% (for example 0-20wt% or 1-20wt%, 4-18 or 7-15wt% or 9-12wt%) and 0-12wt% (1-10wt% for example, such as 5wt%) saltcake and the glauberite of the halite (sodium-chlor) of 0-12wt% (for example 1-18 or 2-10wt%, such 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, for example 1g/L ~ 400g/L, 10 ~ 100g/L, 20 ~ 80g/L, especially 40 ~ 45g/L, the particularly calcium chloride water about 45g/L; Or except containing calcium chloride, also contain for example sodium-chlor of one or more other salt, magnesium chloride, the aqueous solution of optional inevitable impurity, for example it can be the aqueous solution that contains 1 ~ 100g/L calcium chloride and 1 ~ 100g/L sodium-chlor, the aqueous solution that for example contains 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium-chlor, the aqueous solution that contains 30 ~ 60g/L calcium chloride and 20 ~ 50g/L sodium-chlor, the aqueous solution that more preferably contains 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium-chlor is more preferably the aqueous solution that contains 40 ~ 47g/L calcium chloride (for example 45g/L calcium chloride) and 35 ~ 45g/L sodium-chlor (for example 42g/L); Or the waste liquid of the chloride containing calcium that produces in the Chemical Manufacture, for example the clear calcium liquid of ammonia alkali is (namely from the CaCl that contains in the ammonia alkali process
2Waste liquid) etc. waste liquid.Can in dilution or undiluted situation, be used in the described conversion exploitation from this waste ammonia-soda solution of the high density in the ammonia alkali technique, be used in the described conversion exploitation after preferably being diluted among the application the concentration for the aqueous solution defined of chloride containing calcium.After through dilution, this waste ammonia-soda solution can be or become the aqueous solution that contains 1 ~ 100g/L calcium chloride and 1 ~ 100g/L sodium-chlor, the aqueous solution that for example contains 20 ~ 80g/L calcium chloride and 20 ~ 80g/L sodium-chlor, the aqueous solution that contains 30 ~ 60g/L calcium chloride and 20 ~ 50g/L sodium-chlor, the aqueous solution that more preferably contains 30 ~ 50g/L calcium chloride and 30 ~ 50g/L sodium-chlor is more preferably the aqueous solution that contains 40 ~ 47g/L calcium chloride (for example 45g/L calcium chloride) and 35 ~ 45g/L sodium-chlor (for example 42g/L).By using the waste liquid of ammonia alkali technique, solved the difficult problem that disposes waste liquid that Chemical Manufacture for example faces in the ammonia alkali technique.
In a preferred implementation, when the temperature of salt mine underground mining point is slightly high for example 35 ~ 70 ℃, more preferably 40 ~ 60 ℃, more preferably 50 ~ 55 ℃ the time, the aqueous solution of chloride containing calcium is directly annotated well with room temperature.For example be lower than 25 ℃ or when being lower than 20 ℃, the temperature of the aqueous solution of chloride containing calcium was warmed up to 30 ~ 90 ℃ before annotating well when the temperature of salt mine underground mining point is slightly low, preferred 35 ~ 70 ℃, more preferably 40 ~ 60 ℃, more preferably annotate well after 50 ~ 55 ℃.
In general, because underground rock salt component content is extremely inhomogeneous, add that the subsurface geology situation is complicated, the ore deposit halogen quality 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 (for example about 298g/L); Na
2SO
4Content generally exists〉12g/L-30g/L, preferred 12.5-27g/L, more preferably 17-25g/L, more more preferably 19-24g/L, most preferably 20-23g/L scope (for example about 22g/L), other impurity (comprising calcium sulfate, magnesium chloride) content is general＜7g/L, preferably＜5g/L, more preferably＜3g/L, more more preferably＜1g/L, most preferably＜0.5g/L or even be 0g/L, the application claims this class bittern for " high caldo ".The composition of the composition of " calcium sulfate type well mine salt " fresh water mining brine is: NaCl content is generally at 250-330g/L, preferred 270-322g/L, more preferably 280-318g/L, most preferably 290-313g/L scope (for example about 310g/L); Na
2SO
4Content is 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 (for example about 2.6g/L); CaSO
4Content is 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 (for example about 5.5g/L).
But, no matter sodium sulfate type salt well ore deposit, or calcium sulfate type salt well ore deposit, glauberite often contained.When water flooding recovery, fresh water at first mixes with the nearly saturated ore deposit of the high nitre halogen that exists in the salt chamber, more preferential fast dissolving sodium-chlor and saltcake, thereby so that the sodium sulphate content in the solution comparatively fast reaches more than the 12g/L, glauberite is difficult for dissolvedly in such solution, thereby glauberite can't be utilized.
The application not only is particularly suitable for the high rock salt of glauberite content (being well mine salt), also is suitable for low-grade glauberite, namely contains the glauberite of low glauberite content (being lower than 20wt%, for example 0.1-20wt%).Certainly, most preferably be applicable to the high rock salt of glauberite content (glauberite (CaSO
4Na
2SO
4) average content is 1-15wt%, preferred 2-10wt%, more preferably 3-8wt%, especially 4-6wt%).
Composition is not identical in the waste ammonia-soda solution that each ammonia alkali enterprise produces.In the present invention, take the soda ash output of 600,000 t/ as the basis, the waste ammonia-soda solution amount generally is 5-13m
3/ t soda ash (butt), more general 7-11m
3/ t soda ash, especially 8-10m
3/ t soda ash, for example about 9m
3/ t soda ash, the composition of waste ammonia-soda solution is: CaCl
2Content is generally at 80-130g/L (butt), preferred 90-120g/L, more preferably 95-115g/L, most preferably 100-110g/L scope (for example about 105g/L); NaCl content generally is at 30-70g/L (butt), more general 40-60g/L, especially 45-55g/L (for example about 50g/L); Ammonia alkali waste residue amount is generally at 250-335kg/t soda ash (butt), more general 270-330kg/t soda ash, especially 290-325kg/t soda ash, for example about 320kg/t soda ash (butt)." t " expression " ton ".
When using above-mentioned waste ammonia-soda solution, can directly use it, or preferably, be used after it is diluted, dilution is rear so that CaCl
2Content generally be for example 10 ~ 100g/L, 20 ~ 80g/L, 30 ~ 70g/L, especially 35 ~ 60g/L, particularly 40 ~ 50g/L, most preferably about 45g/L.
The disclosed full content of the applicant's CN102205979A is introduced among the application as a reference, just as describing fully 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, only provided calcium chloride content, then the sodium chloride content of this solution is to be lower than 1wt% or 0-1wt%, for example is lower than 0.5wt%, and other foreign matter content is 0-2wt%, such as 1wt%.If provided simultaneously calcium chloride content and sodium chloride content, then can contain other impurity of a small amount of (for example 0-2wt%, such as 1wt%).
Preferably, in this application, the aqueous solution of chloride containing calcium is from the waste ammonia-soda solution in the ammonia alkali technique or resulting through dilution by the waste ammonia-soda solution in the ammonia alkali technique.
Effect of the present invention:
According to the present invention, can annotate the mode that well is adopted halogen with the fresh water in existing rock salt resource ore deposit, the aqueous solution with chloride containing calcium replaces fresh water to exploit, in the soluble salt resources such as exploitation sodium-chlor, saltcake, the glauberite of association indissoluble also is converted to soluble NaCl in the rock salt, and obtain exploitation and utilize, thereby successfully broken the present situation that the association glauberite can not be exploited utilization, realized improving the purpose of the utilization ratio of rock salt resource.
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 for rock salt mining, association glauberite resource full extraction in the rock salt can be utilized, improve the comprehensive utilization ratio of rock salt resource, solved the technical barrier that association glauberite resource is not utilized in the rock salt.
2, the aqueous solution of chloride containing calcium can be the waste liquid (need guarantee the rock salt resource not to be produced to pollute) that produces chloride containing calcium in the Chemical Manufacture, and for example the clear calcium liquid of ammonia alkali is (for example from the CaCl that contains in the ammonia alkali process
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 simultaneously significant economic benefit.
3, the applicant is at the initial stage that carries out an invention CN102205979A, and increase tens00000000 benefit every year newly, and along with expansion scale and production capacity, economic benefit is more remarkable.Therefore, the application has reason to believe that the following invention of implementing on a large scale among the application also can produce significant economic benefit.
Description of drawings:
Fig. 1 shows process flow diagram of the present invention, and it comprises the aqueous solution of preparing chloride containing calcium; Annotate well; Dissolving (glauberite is dissolved as sl. sol. calcium sulfate and soluble sodium sulfate), reaction (dissolving the calcium chloride reaction in the aqueous solution of the sodium sulfate that and chloride containing calcium), sedimentation (the calcium sulfate sedimentation of reaction generation); Brine mining; Obtain at last required bittern.
Embodiment
Below be described more specifically the present invention.
In the method for the invention, take the rock salt mine as example, the aqueous solution of chloride containing calcium is injected the mine of exploitation rock salt, at first, when the soluble salts such as sodium-chlor, saltcake were dissolved, association was also decomposed by molten drench in the rock salt, and obtained soluble sodium sulfate.Secondly, be dissolved in the calcium chloride generation chemical reaction that itself contains in sodium sulfate and the solution in the solution, generation CaSO
4Precipitation and soluble NaCl, CaSO
4To mine bottom, the sodium-chlor that reaction generates then along with ore deposit halogen together and after the exploitation out, is used again through natural subsidence.Meanwhile, by the reaction of excessive calcium chloride and sodium sulfate, removed the sodium sulfate in the solution, so that the solution of exploitation rock salt is chloride-calcium type bittern; Perhaps by inexcessive calcium chloride and the reaction of sodium sulfate, remove the part of sulfuric acid sodium in the solution, so that the solution of exploitation rock salt is low nitre (sodium sulphate content is less than 12g/L) bittern, solution environmental has promoted again the molten drench of glauberite to decompose like this, thereby guarantees that glauberite all is converted exploitation in the rock salt.
In the method for the invention, in conjunction with physical and chemical principle, principles of hydrodynamics and material diffusion and mass transfer rule, glauberite corrosion process in the aqueous solution (hereinafter to be referred as calcium liquid) of chloride containing calcium can roughly be 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 having begun dissolving, the glauberite dissolution rate is fast, the Na that gathers around the glauberite
2SO
4Concentration raises gradually.
(2) by diffusion, the glauberite drench goes out Na
+, SO
4 2-And the Ca of trace
2+In calcium liquid, carry out mass transfer, transmitted to the low ion concns district by high density.
(3) conversion reaction, the SO that the molten drench of glauberite goes out
4 2-And the Ca of trace
2+In mass transfer, the Ca that will contain with calcium liquid Central Plains
2+Under hydration, generate sl. sol. crystalline hydrate CaSO
42H
2O; And molten drench goes out Na
+With Cl in the calcium liquid
-Generate NaCl.At this moment, form a large amount of solution pervasion passages on glauberite surface and inside, volumetric expansion, glauberite is broken also to be peeled off, and forms new interface and contacts with calcium liquid, and increased and calcium liquid contact area, has promoted the dissolving of glauberite.
Because rock salt mining is a dynamic successive processes, the nearly saturated ore deposit of sodium-chlor halogen (being nearly saturated bittern) is constantly exploited out, and undersaturated calcium chloride solution is constantly replenished, so that glauberite is under the calcium chloride solution environment all the time, glauberite is molten drench constantly, thereby all glauberite all is converted exploitation out.
Embodiment:
Illustrate:
(1) the rock salt component of various places is different, and content is different, and therefore, among the embodiment, sodium sulfate type rock salt composition is take certain domestic salt mine as example herein: the NaCl average content is as 52.86%, association component 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 take certain domestic salt mine as example: the NaCl average content is as 58.46%, association component 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 inhomogeneous, add that the subsurface geology situation is complicated, among the embodiment, supposes that each component of rock salt mixes.
(3) calcium chloride solution can be the aqueous solution that contains a certain amount of calcium chloride, with CaCl
220g/L, 40g/L or 80g/L solution are example; Also can be for containing the aqueous solution of a certain amount of calcium chloride and sodium-chlor, to contain CaCl
2The solution of 40g/L (or 50g/L) and NaCl 40g/L is example.
(4) production factor gets 0.9, and the ore deposit halogen total salt content of exploitation is in 320g/L.
(5) during practical application, should according to the practical situation of each mine, on the basis that theory is calculated, be revised by industrial experimentation, then production application.
Embodiment 1: with 1m
3Contain CaCl
2Solution (or aqueous solution) injection sodium sulfate type rock salt mine for 20g/L, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in first in the water (water that ie in solution is contained), simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, at the bottom of the sedimentation, produce simultaneously soluble sodium-chlor, be dissolved in the water, along with bittern flows, also has a small amount of saltcake dissolving.After enough time sedimentation in 1 month, exploit out about 0.9m
3NaCl 316g/L, Na
2SO
4The low nitre ore deposit halogen (being bittern) of 4g/L.
Embodiment 2: with 1m
3Contain CaCl
2Solution injection sodium sulfate type rock salt mine for 40g/L, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.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: with 1m
3Contain CaCl
2Solution injection sodium sulfate type rock salt mine for 80g/L, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.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: with 1m
3Contain CaCl
250g/L, the solution of NaCl 40g/L (from the waste liquid of ammonia alkali production technique) injects sodium sulfate type rock salt mine, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.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: with 1m
3Contain CaCl
2Solution injection calcium sulfate type rock salt mine for 40g/L, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.After enough time sedimentation in 1 month, exploit out about 0.9m
3NaCl 295.5g/L, CaCl
224.5g/L ore deposit halogen.
Embodiment 6: with 1m
3Contain CaCl
2Solution injection sodium sulfate type rock salt mine for 80g/L, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.After 1 month enough time sedimentation, exploit out about 0.9m
3NaCl 259g/L, CaCl
2The ore deposit halogen of 61g/L.
Embodiment 7: with 1m
3Contain CaCl
240g/L, the solution of NaCl 40g/L injects sodium sulfate type rock salt mine, 50 ℃ in down-hole left and right sides environment of rock salt, the soluble salt such as sodium-chlor and saltcake is dissolved in the water first, simultaneously, glauberite is also resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, calcium sulfate precipitation is in the down-hole, sodium sulfate then is dissolved in the water, at this moment, dissolve the sodium sulfate that all with solution in original calcium chloride reaction, generate slightly soluble calcium sulfate, sedimentation is low, produce simultaneously soluble sodium-chlor, be dissolved in the water, the calcium chloride that cannot react completely is along with ore deposit halogen is exploited out.After 1 month enough time sedimentation, exploit out about 0.9m
3NaCl 294.2g/L, CaCl
225.8g/L ore deposit halogen.
Claims (10)
1. the conversion reoovery method that contains the rock salt of glauberite resources, the method comprises: the aqueous solution of chloride containing calcium is injected the mine that contains glauberite resources of exploiting rock salt or the mine that injects low-grade glauberite, glauberite in the ore deposit is resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, wherein the calcium sulfate precipitation of segregation is in the shaft bottom, sodium sulfate then is dissolved in the aqueous solution, and dissolve the sodium sulfate that all with the aqueous solution of chloride containing calcium in the calcium chloride reaction, generate slightly soluble calcium sulfate and also be deposited in the shaft bottom, simultaneous reactions produces soluble sodium-chlor, at last, behind the dissolution process of for some time (for example 6 hours-2 months), exploitation ore removal halogen.
2. method according to claim 1, wherein, the aqueous solution of chloride containing calcium is that calcium chloride concentration is the calcium chloride water of 1g/L ~ 130g/L, preferred 10 ~ 100g/L, or also contains the aqueous solution of sodium-chlor and/or magnesium chloride and other impurity of choosing wantonly except the calcium chloride that contains above-mentioned concentration; Preferably, it is the aqueous solution that contains the sodium-chlor of the calcium chloride of 1g/L ~ 130g/L, preferred 10 ~ 100g/L and 1g/L ~ 100g/L, preferred 10 ~ 90g/L.
3. method according to claim 2, wherein, the aqueous solution of chloride containing calcium is that calcium chloride concentration is the calcium chloride water of 30 ~ 60g/L, or contains the aqueous solution of the sodium-chlor of the calcium chloride of 30g/L ~ 60g/L and 20 ~ 50g/L; Preferably, the aqueous solution of chloride containing calcium is to contain the aqueous solution of 40 ~ 50g/L calcium chloride or contain 40 ~ 50g/L calcium chloride and the aqueous solution of 20 ~ 50g/L sodium-chlor.
4. according to claim 1 method, wherein glauberite resources is the glauberite of the association of sodium sulfate type or calcium sulfate type rock salt mineral reserve, wherein the content of glauberite in rock salt is 1-15wt%, preferred 2-10wt%; Or low-grade glauberite, wherein the content of glauberite in the salt resource is less than 20wt%.
5. each described method according to claim 1 ~ 4, wherein, by molar weight, calcium chloride when annotating well in the aqueous solution of maintenance chloride containing calcium is excessive with respect to dissolving the sodium sulfate that, thereby remove the sodium sulfate that dissolves in the solution fully by precipitation, so that the solution of exploitation rock salt is always chloride-calcium type bittern.
6. each described method according to claim 1 ~ 4, wherein the aqueous solution of chloride containing calcium is from the waste ammonia-soda solution in the ammonia alkali technique or resulting through dilution by the waste ammonia-soda solution in the ammonia alkali technique.
7. the aqueous solution of chloride containing calcium is for the purposes of the conversion exploitation of the rock salt that contains glauberite resources.
8. purposes according to claim 7, wherein glauberite resources is the glauberite of the association of sodium sulfate type or calcium sulfate type rock salt mineral reserve, wherein the content of glauberite in rock salt is 1-15wt%, preferred 2-10wt%; Or low-grade glauberite, wherein the content of glauberite in the salt resource is less than 20wt%.
9. according to claim 7 or 8 purposes, wherein the aqueous solution of chloride containing calcium is that calcium chloride concentration is the calcium chloride water of 1g/L ~ 130g/L, preferred 10 ~ 100g/L, or also contains the aqueous solution of sodium-chlor and/or magnesium chloride and other impurity of choosing wantonly except the calcium chloride that contains above-mentioned concentration; Preferably, it is the aqueous solution that contains the sodium-chlor of the calcium chloride of 1g/L ~ 130g/L, preferred 10 ~ 100g/L and 1g/L ~ 100g/L, preferred 10 ~ 90g/L.
10. the rock salt that contains glauberite resources utilizes the conversion reoovery method of ammonia-soda process waste liquid, and the method may further comprise the steps:
1), utilizes the solvay soda process standby alkali (Na of making from brine
2CO
3), obtain solid sodium carbonate, produce simultaneously waste ammonia-soda solution and ammonia alkali waste residue,
2), waste ammonia-soda solution is injected the mine that contains glauberite resources of exploiting rock salt or the mine that injects low-grade glauberite in dilution or undiluted situation, glauberite in the ore deposit is resolved into sl. sol. calcium sulfate and soluble sodium sulfate by molten drench under the environment of calcium chloride solution, wherein the calcium sulfate precipitation of segregation is in the shaft bottom, sodium sulfate then is dissolved in the aqueous solution, and dissolve the sodium sulfate that all with the aqueous solution of chloride containing calcium in the calcium chloride reaction, generate slightly soluble calcium sulfate and also be deposited in the shaft bottom, simultaneous reactions produces soluble sodium-chlor, behind the dissolution process of for some time (for example 6 hours-2 months), exploitation ore removal halogen.
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| 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 |
| CN107406267A (en) * | 2015-03-02 | 2017-11-28 | 索尔维公司 | Method for manufacturing sodium-chloride water 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 |
| CN112723391A (en) * | 2021-02-24 | 2021-04-30 | 彭赛军 | Process for co-producing soda ash and calcium sulfate from ammonium bicarbonate and glauberite tailings |
| CN113482577A (en) * | 2021-07-21 | 2021-10-08 | 江苏淮盐矿业有限公司 | Bittern purification and collection method |
| 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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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 |
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