CN104192872A - Method for directly preparing sodium carbonate from underground brine - Google Patents
Method for directly preparing sodium carbonate from underground brine Download PDFInfo
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- CN104192872A CN104192872A CN201410364742.2A CN201410364742A CN104192872A CN 104192872 A CN104192872 A CN 104192872A CN 201410364742 A CN201410364742 A CN 201410364742A CN 104192872 A CN104192872 A CN 104192872A
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- China
- Prior art keywords
- bittern
- ammonia
- soda ash
- soda
- solid
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Links
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 69
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 60
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000012267 brine Substances 0.000 title claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 32
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 28
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 28
- 238000007670 refining Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 241001131796 Botaurus stellaris Species 0.000 claims description 100
- 235000017550 sodium carbonate Nutrition 0.000 claims description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 42
- 239000002002 slurry Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 238000009621 Solvay process Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 17
- 235000011089 carbon dioxide Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical class [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000003337 fertilizer Substances 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 24
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 24
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000011575 calcium Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 235000011116 calcium hydroxide Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- -1 key is Chemical compound 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229960001708 magnesium carbonate Drugs 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Fertilizers (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for directly preparing sodium carbonate from underground brine. The method comprises the steps of reacting by using an ammonia process to remove most of magnesium ions in the brine; and then, carrying out secondary refining by using an intermediate material generated in the intermediate process of sodium carbonate production to remove calcium and magnesium ions, wherein the refined brine is used as a raw material for preparing sodium carbonate, and a magnesium hydroxide sediment generated in the process of removing the magnesium ions through reacting by using the ammonia process is used as a magnesium hydroxide product to be sold after being separated and dried. Through comprehensive utilization of resources, saturated brine can be directly used for sodium carbonate production after being refined, the salt yield of the brine is increased by more than 15%, the yield of a salt pan is increased by about more than 50%, meanwhile, components such as calcium and magnesium ions in the brine are also effectively utilized, and the advantage of cyclic economy is sufficiently exerted.
Description
Technical field
The present invention relates to subsurface brine comprehensive utilization technique field, be specifically related to a kind of method of utilizing subsurface brine directly to prepare soda ash.
Background technology
Undergroundly at side, Bohai Sea Gulf contain abundant subsurface brine resource, can utilize bittern to carry out soda ash as alkaline raw material substitution crude salt and produce and can obviously reduce outsourcing crude salt consumption, reduce soda ash manufacturing cost.
Because contain a large amount of impurity such as calcium ions and magnesium ions in subsurface brine, utilize bittern to carry out soda ash production as alkaline raw material and there is larger technical bottleneck, as follows: the impurity such as a large amount of calcium that contain in bittern, magnesium ion, without the refining raw material of directly producing as soda ash, can in alkali producing process, produce a large amount of calcium magnesium precipitates, cause that pipeline and tower scab.Calcium magnesium precipitate remains in product and causes that Water Insoluble in Soda increases, and affects soda ash quality simultaneously.
Therefore, in current traditional solvay soda process soda ash production, the method for salt refining is lime-soda process and two kinds of methods of lime volatile salt method.
(1) lime-soda process is that (effective constituent is Ca (OH) with milk of lime
2) remove the magnesium ion in crude brine, then with soda ash, remove the calcium ion in crude brine.
(2) lime ammonium carbonate method is to remove the magnesium ion in crude brine with milk of lime.Then with volatile salt, remove the calcium ion in crude brine.
But, although these two kinds of methods all can be used for the refining of bittern, but because of calcium ions and magnesium ions foreign matter content in bittern too high, in treating process, can consume the raw materials such as a large amount of unslaked lime and soda ash, and the refining calcium magnesium precipitate producing can only be as waste discharge, cause that refining cost is too high, can not produce economic benefit.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of utilizing subsurface brine directly to prepare soda ash, and the comprehensive utilization that it can realize subsurface brine, greatly reduces production cost, thereby eliminates defect in above-mentioned background technology.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Utilize subsurface brine directly to prepare a method for soda ash, step is as follows:
S1, subsurface brine is evaporated, obtaining concentration is the dense bittern of 22-23 degree Beaume;
In S2, the dense bittern that obtains to step S1, add solid salt, obtain saturated bittern after changing salt;
S3, the saturated bittern that step S2 is obtained enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, obtain ammonia bittern slurries, and described ammonia bittern slurries are clarified, and filter to isolate magnesium hydroxide solid, and obtain filtrate is ammonia bittern simultaneously;
S4, the ammonia bittern that step S3 is obtained enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, in obtaining and bittern slurries, to in described, add solid powder salt with bittern slurries, then clarify, filter to isolate the carbonate of calcium ions and magnesium ions, obtain the refining ammonia bittern of filtrate simultaneously;
S5, the refining ammonia bittern that step S4 is obtained utilize ammonia-soda process soda ash.
The technique of the ammonia-soda process soda ash of step S5 is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda ash production technique, with the crystallization of carbonic acid gas solid/liquid/gas reactions Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after separation.
As a kind of preferred technical scheme, in described step S3, inhale temperature in ammonia reactor and maintain 60-80 ℃.
As a kind of preferred technical scheme, in described step S3, utilize press filtration mode to filter to isolate magnesium hydroxide solid.
As a kind of preferred technical scheme, in described step S3, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid is dried, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
As a kind of preferred technical scheme, in described step S4, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixture body, and wherein the volume ratio of carbonic acid gas is 38%-40%.
As a kind of preferred technical scheme, in described step S4, the calcium magnesium salts filtering to isolate is washed, and solid is dried and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
Principle of the present invention is as follows:
To concentration, be to add solid salt in the dense bittern of 22-23 degree Beaume, sodium chloride concentration in bittern is mentioned to state of saturation, to improve the concentration of the sodium-chlor in carbonation reaction, improve the transformation efficiency of sodium-chlor, then in inhaling ammonia reactor, pass into ammonia, key is, ammonia necessarily can not contain carbonic acid gas, if contain carbon dioxide gas in ammonia, can produce the carbonate compound precipitation of calcium ions and magnesium ions in inhaling ammonia react process, affect magnesium hydroxide purity, reaction equation is: Mg
2++ 2NH
4oH=Mg (OH)
2↓+2NH
4 +, can remove 85～95% magnesium ion, a large amount of magnesium hydrate precipitates of generation are sold as product after separation is dry, and then input carbonization reactor, pass into carbon dioxide containing gas (volume ratio is 38%-40%) simultaneously, carry out the reaction of decalcification magnesium ion, reaction equation is Ca
2++ (NH
4)
2cO
3=CaCO
3↓+2NH
4 +, Mg
2++ (NH
4)
2cO
3=MgCO
3↓+2NH
4 +, there is very large technical barrier in this step, , magnesiumcarbonate is slightly soluble in water, cause the purity of sode product in later stage very low, contriver is through after a large amount of experiments repeatedly, final discovery, this step will in and bittern slurries add solid powder salt, under the state of high sodium chloride concentration and high carbon acid ammonium concentration, the solubleness of magnesiumcarbonate is very low, can precipitate and remove smoothly, simultaneously, after ammonia bittern absorbing carbon dioxide, the solubleness of sodium-chlor improves, at this, add solid powder salt to dissolve, the concentration of sodium-chlor in can improving and in bittern, improve the transformation efficiency of sodium-chlor in carbonation reaction, the calcium magnesium precipitate producing is sold as ca and mg fertilizer product.
Contriver is according to subsurface brine analysis of components, concrete feature in conjunction with solvay soda process soda ash production technique, through a large amount of experiments repeatedly, determine to adopt ammonia process reaction to remove in bittern after most of magnesium ion, the intermediate material of producing pilot process through soda ash again carries out secondary refining to be removed after calcium ions and magnesium ions, and refining bittern is used as alkaline raw material.Ammonia process reaction removes the magnesium hydrate precipitate of magnesium ion process generation and as magnesium hydroxide products, sells after separation is dry.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, by the calcium ions and magnesium ions in bittern being removed with ammonia and volatile salt, refining bittern can substitute solid crude salt and use as alkaline raw material.
2, the magnesium hydrate precipitate producing in primary purification process can obtain highly purified magnesium hydroxide products after separation, and the calcium magnesium precipitate producing in secondary refining process can obtain ca and mg fertilizer product after separation, can produce good economic benefit.
3, the sodium ion in bittern and calcium ions and magnesium ions have obtained effective utilization, have given full play to the effect of recycling economy.
The present invention is by comprehensive utilization of resources, after saturated bittern can being refined, be directly used in soda ash and produce, bittern produces salt amount to be increased more than 15%, and salt pan output increases approximately more than 50%, also effectively utilize the compositions such as calcium ions and magnesium ions in bittern simultaneously, given full play to the advantage of recycling economy.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Embodiment 1
Utilize subsurface brine directly to prepare a method for soda ash, technical process is as shown in Figure 1, as follows:
S1, subsurface brine is evaporated, obtaining concentration is the dense bittern of 22 degree Beaume;
In S2, the dense bittern that obtains to step S1, add solid salt, obtain saturated bittern after changing salt;
S3, the saturated bittern that step S2 is obtained enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 60 ℃, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilize press filtration mode to filter to isolate magnesium hydroxide solid, obtain filtrate is ammonia bittern simultaneously, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid is dried, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern that step S3 is obtained enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and in obtaining, with bittern slurries, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixture body, and wherein the volume ratio of carbonic acid gas is 38%; By adding solid powder salt with bittern slurries in described, then clarify, filter to isolate calcium magnesium salts, obtain the refining ammonia bittern of filtrate simultaneously, the calcium magnesium salts filtering to isolate is washed, and solid is dried and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S5, the refining ammonia bittern that step S4 is obtained utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda ash production technique, with the crystallization of carbonic acid gas solid/liquid/gas reactions Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after separation.
Embodiment 2
Utilize subsurface brine directly to prepare a method for soda ash, technical process is as shown in Figure 1, as follows:
S1, subsurface brine is evaporated, obtaining concentration is the dense bittern of 23 degree Beaume;
In S2, the dense bittern that obtains to step S1, add solid salt, obtain saturated bittern after changing salt;
S3, the saturated bittern that step S2 is obtained enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 80 ℃, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilize press filtration mode to filter to isolate magnesium hydroxide solid, obtain filtrate is ammonia bittern simultaneously, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid is dried, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern that step S3 is obtained enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and in obtaining, with bittern slurries, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixture body, and wherein the volume ratio of carbonic acid gas is 40%; By adding solid powder salt with bittern slurries in described, then clarify, filter to isolate calcium magnesium salts, obtain the refining ammonia bittern of filtrate simultaneously, the calcium magnesium salts filtering to isolate is washed, and solid is dried and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S5, the refining ammonia bittern that step S4 is obtained utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda ash production technique, with the crystallization of carbonic acid gas solid/liquid/gas reactions Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after separation.
Embodiment 3
Utilize subsurface brine directly to prepare a method for soda ash, technical process is as shown in Figure 1, as follows:
S1, subsurface brine is evaporated, obtaining concentration is the dense bittern of 23 degree Beaume;
In S2, the dense bittern that obtains to step S1, add solid salt, obtain saturated bittern after changing salt;
S3, the saturated bittern that step S2 is obtained enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 70 ℃, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilize press filtration mode to filter to isolate magnesium hydroxide solid, obtain filtrate is ammonia bittern simultaneously, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid is dried, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern that step S3 is obtained enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and in obtaining, with bittern slurries, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixture body, and wherein the volume ratio of carbonic acid gas is 39%; By adding solid powder salt with bittern slurries in described, then clarify, filter to isolate calcium magnesium salts, obtain the refining ammonia bittern of filtrate simultaneously, the calcium magnesium salts filtering to isolate is washed, and solid is dried and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S5, the refining ammonia bittern that step S4 is obtained utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda ash production technique, with the crystallization of carbonic acid gas solid/liquid/gas reactions Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after separation.
Embodiment 4
Bittern is delivered to multiple solarization evaporation in multiple threshing ground by proposing the extraction of halogen pump by pipeline, bittern concentration enrichment to 22 degree Beaume, approach saturated after, add solid salt to mix, bittern is refined after pipeline is delivered to soda ash production equipment district internalization salt, obtain saturated bittern, then through twice refining removing, be sent to carbonation process alkaline after calcium ions and magnesium ions and use.The precipitation producing in treating process is respectively used to produce the products such as magnesium hydroxide, ca and mg fertilizer.Concrete technology flow process is described below:
Through multiple solarization, approach saturated bittern and add salt, change make after salt saturated bittern be delivered in de-magging tower with soda ash production process in the ammonia of carbon dioxide removal react that (reaction equation is: Mg
2++ 2NH
4oH=Mg (OH)
2↓+2NH
4+), remove after the magnesium ion of 85-95%, then be delivered to and in carbonating tower, pass into carbon dioxide gas and carry out the reaction of decalcification magnesium ion [reaction equation is Ca
2++ (NH
4)
2cO
3=CaCO
3↓+2NH
4+, Mg
2++ (NH
4)
2cO
3=MgCO
3↓+2NH
4+], reaction solution is delivered to carbonization process alkaline and uses after clarification.A large amount of magnesium hydrate precipitates that primary purification process produces are sold as product after separation is dry.The calcium magnesium precipitate producing in secondary refining process is sold as ca and mg fertilizer product.
Material balance
With embodiment 3, by application man-year, produce design in 8000 hours, company is multiple, and threshing ground is per hour can produce 62.50m
323 degree Beaume approach saturated bittern, and the bittern after multiple solarization again and 400m
3/ h is 462.5m without the rear flow of bittern mixing of multiple solarization
3/ h, mixes going of bittern salt and uses.Through accounting, year can be used 320,000 tons of liquid salt, 4.16 ten thousand tons, coproduct hydrogen magnesium oxide.
Economic and Efficiency Analysis
Through accounting, to use the salt deduction of bringing in every side's mixing bittern to refine expense and equipment amortization working cost etc. and can produce the economic benefit of 7.31 yuan, a year generation economic benefit is 2703.49 ten thousand yuan.
Use 1m
3mixing bittern can by-product 11.25kg magnesium hydroxide products in treating process, this in project year coproduct hydrogen magnesium oxide be 4.16 ten thousand tons.The production cost of magnesium hydroxide per ton is temporarily by 2000 yuan of calculating, sale price per ton is carried out Conservative estimation by 4000 yuan, magnesium hydroxide profit per ton is 2000 yuan, and a year generation economic benefit is 8,320 ten thousand yuan, and this project is estimated to produce overall economic efficiency and added up to 11023.49 ten thousand yuan.
Remarks: because the cost recovery (being mainly low-pressure steam and Wingdale, coke consumption) of ammonia in magnesium hydroxide production process has counted bittern cost, for this reason, no longer count magnesium hydroxide products cost.
Comparative example 1
By application man-year, produce design in 8000 hours, company is multiple, and threshing ground is per hour can produce 62.50m
323 degree Beaume approach saturated bittern, then bittern are used conventional methods to alkaline: with milk of lime, (effective constituent is Ca (OH)
2) remove the magnesium ion in crude brine, then with soda ash, remove the calcium ion in crude brine.
Year produces Economic and Efficiency Analysis
Comparative example 2
By application man-year, produce design in 8000 hours, company is multiple, and threshing ground is per hour can produce 62.50m
323 degree Beaume approach saturated bittern, then bittern are used conventional methods to alkaline: lime ammonium carbonate method is to remove the magnesium ion in crude brine with milk of lime.Then with volatile salt, remove the calcium ion in crude brine.
Year produces Economic and Efficiency Analysis
From embodiment 3, comparative example 1, can obviously see with comparative example 2 economic benefit calculation table, adopt the technical program to process subsurface brine, can greatly improve a year economic benefit.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and the structural improvement of having done, all falls among protection scope of the present invention.
Claims (7)
1. utilize subsurface brine directly to prepare a method for soda ash, it is characterized in that: step is as follows:
S1, subsurface brine is evaporated, obtaining concentration is the dense bittern of 22-23 degree Beaume;
In S2, the dense bittern that obtains to step S1, add solid salt, obtain saturated bittern after changing salt;
S3, the saturated bittern that step S2 is obtained enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, obtain ammonia bittern slurries, and described ammonia bittern slurries are clarified, and filter to isolate magnesium hydroxide solid, and obtain filtrate is ammonia bittern simultaneously;
S4, the ammonia bittern that step S3 is obtained enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, in obtaining and bittern slurries, to in described, add solid powder salt with bittern slurries, then clarify, filter to isolate calcium magnesium salts, obtain the refining ammonia bittern of filtrate simultaneously;
S5, the refining ammonia bittern that step S4 is obtained utilize ammonia-soda process soda ash.
2. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, is characterized in that: in described step S3, inhale temperature in ammonia reactor and maintain 60-80 ℃.
3. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, is characterized in that: in described step S3, utilize press filtration mode to filter to isolate magnesium hydroxide solid.
4. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, it is characterized in that: in described step S3, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid is dried, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
5. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, is characterized in that: in described step S4, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixture body, and wherein the volume ratio of carbonic acid gas is 38%-40%.
6. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, it is characterized in that: in described step S4, the calcium magnesium salts filtering to isolate is washed, and solid is dried and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
7. a kind of method of utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, it is characterized in that: the technique of the ammonia-soda process soda ash of step S5 is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda ash production technique, with the crystallization of carbonic acid gas solid/liquid/gas reactions Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after separation.
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| CN105712382A (en) * | 2016-04-14 | 2016-06-29 | 中国中轻国际工程有限公司 | Technology for producing sodium bicarbonate from mirabilite |
| CN113403151A (en) * | 2021-06-17 | 2021-09-17 | 浙江新益印染有限公司 | Method for removing colloid on dyed cloth surface of cotton fabric |
| WO2024192753A1 (en) * | 2023-03-23 | 2024-09-26 | 广东邦普循环科技有限公司 | Method for extracting lithium from salt lake |
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