CN104192872B - A kind of method utilizing subsurface brine directly to prepare soda ash - Google Patents
A kind of method utilizing subsurface brine directly to prepare soda ash Download PDFInfo
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- CN104192872B CN104192872B CN201410364742.2A CN201410364742A CN104192872B CN 104192872 B CN104192872 B CN 104192872B CN 201410364742 A CN201410364742 A CN 201410364742A CN 104192872 B CN104192872 B CN 104192872B
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- Prior art keywords
- bittern
- ammonia
- soda ash
- soda
- magnesium
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 67
- 235000017550 sodium carbonate Nutrition 0.000 title claims abstract description 42
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 42
- 239000012267 brine Substances 0.000 title claims abstract description 34
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 120
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 103
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 33
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 27
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 27
- 238000007670 refining Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 23
- 239000002002 slurry Substances 0.000 claims description 21
- 238000009621 Solvay process Methods 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 16
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical class [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 15
- 235000011089 carbon dioxide Nutrition 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
- 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
- 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
- 238000001914 filtration Methods 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
- 239000002243 precursor Substances 0.000 claims 1
- 239000000376 reactant Substances 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
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 15
- 239000002244 precipitate Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002156 mixing 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
- 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
- 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 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
- 238000011049 filling Methods 0.000 description 1
- 230000003760 hair shine Effects 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
A kind of method utilizing subsurface brine directly to prepare soda ash, in employing ammonia process reaction removing bittern after most of magnesium ion, again after the intermediate material of soda manufacture pilot process carries out secondary refining removing calcium ions and magnesium ions, refining bittern uses as alkaline raw material, and the magnesium hydrate precipitate that ammonia process reaction removes the generation of magnesium ion process is sold as magnesium hydroxide products after being separated drying.The present invention passes through comprehensive utilization of resources, be directly used in soda manufacture after saturated bittern can being refined, bittern produces salt amount increases by more than 15%, salt pan output increase about more than 50%, also effectively make use of the compositions such as the calcium ions and magnesium ions in bittern simultaneously, give full play to the advantage of recycling economy.
Description
Technical field
The present invention relates to subsurface brine technical field of comprehensive utilization, be specifically related to a kind of method utilizing subsurface brine directly to prepare soda ash.
Background technology
Contain abundant subsurface brine resource in underground, side, Bohai Sea Gulf, bittern can be utilized to carry out soda manufacture as alkaline raw material substitution crude salt and obviously can reduce outsourcing crude salt consumption, reduce soda ash manufacturing cost.
Because containing impurity such as a large amount of calcium ions and magnesium ions in subsurface brine, utilize bittern to carry out soda manufacture as alkaline raw material and there is larger technical bottleneck, as follows: the impurity such as a large amount of calcium, magnesium ion contained in bittern, without refining directly as the raw material of soda manufacture, a large amount of calcium magnesium precipitates can be produced in alkali producing process, cause pipeline and tower to scab.Calcium magnesium precipitate is residual simultaneously causes Water Insoluble in Soda to increase in the product, affects soda ash quality.
Therefore, in current traditional solvay soda process soda manufacture, the method for salt refining is lime-soda process and lime volatile salt method two kinds of methods.
(1) lime-soda process is that (effective constituent is Ca (OH) with milk of lime
2) removing crude brine in magnesium ion, then with soda ash removing crude brine in calcium ion.
(2) lime ammonium carbonate method is with the magnesium ion in milk of lime removing crude brine.Then with the calcium ion in volatile salt removing crude brine.
But, although these two kinds of methods all can be used for the refining of bittern, but because in bittern, calcium ions and magnesium ions foreign matter content is too high, the raw materials such as a large amount of unslaked lime and soda ash can be consumed in treating process, and the refining calcium magnesium precipitate produced can only as waste discharge, cause refining cost too high, can not economic benefit be produced.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method utilizing subsurface brine directly to prepare soda ash, and it can realize the comprehensive utilization of subsurface brine, greatly reduces production cost, thus 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 to be evaporated, obtain the dense bittern that concentration is 22-23 degree Beaume;
Add solid salt in S2, the dense bittern that obtains to step S1, after changing salt, obtain saturated bittern;
S3, the saturated bittern obtained by step S2 enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, obtain ammonia bittern slurries, are clarified by described ammonia bittern slurries, filter to isolate magnesium hydroxide solid, and obtain filtrate is ammonia bittern simultaneously;
S4, the ammonia bittern obtained by step S3 enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, with bittern slurries in obtaining, solid powder salt is added with bittern slurries in described, then clarify, filter to isolate the carbonate of calcium ions and magnesium ions, obtain filtrate simultaneously and refine ammonia bittern;
S5, the refining ammonia bittern obtained by step S4 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 manufacture 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 being separated.
As the preferred technical scheme of one, in described step S3, inhale temperature in ammonia reactor and maintain 60-80 DEG C.
As the preferred technical scheme of one, in described step S3, press filtration mode is utilized to filter to isolate magnesium hydroxide solid.
As the preferred technical scheme of one, in described step S3, isolated magnesium hydroxide solid is washed, and magnesium hydroxide solid carries out drying, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
As the preferred technical scheme of one, in described step S4, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixed gas, and wherein the volume ratio of carbonic acid gas is 38%-40%.
As the preferred technical scheme of one, in described step S4, the calcium magnesium salts filtered to isolate is washed, and solid carries out drying 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:
Be add solid salt in the dense bittern of 22-23 degree Beaume to concentration, sodium chloride concentration in bittern is mentioned state of saturation, to improve the concentration of the sodium-chlor in carbonation reaction, improve the transformation efficiency of sodium-chlor, then in suction ammonia reactor, pass into ammonia, key is, ammonia necessarily can not contain carbonic acid gas, if containing carbon dioxide gas in ammonia, is inhaling the carbonate compound precipitation that can produce calcium ions and magnesium ions in ammonia react process, affect magnesium hydroxide purity, reaction equation is: Mg
2++ 2NH
4oH=Mg (OH)
2↓+2NH
4 +, can remove the magnesium ion of 85 ~ 95%, a large amount of magnesium hydrate precipitates of generation are sold as product after being separated drying, and then input carbonization reactor, pass into carbon dioxide containing gas (volume ratio is 38%-40%), carry out the reaction of decalcification magnesium ion, reaction equation is Ca simultaneously
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, namely, magnesiumcarbonate is slightly soluble in water, cause the purity of sode product in later stage very low, contriver is after a large amount of experiment 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, removing can be precipitated smoothly, simultaneously, after ammonia bittern absorbing carbon dioxide, the solubleness of sodium-chlor improves, add solid powder salt at this to dissolve, with the concentration of sodium-chlor in bittern in can improving, improve the transformation efficiency of sodium-chlor in carbonation reaction, the calcium magnesium precipitate produced is sold as ca and mg fertilizer product.
Contriver is according to subsurface brine analysis of components, in conjunction with the concrete feature of solvay soda process soda manufacture technique, through a large amount of experiment repeatedly, in decision employing ammonia process reaction removing bittern after most of magnesium ion, again after the intermediate material of soda manufacture pilot process carries out secondary refining removing calcium ions and magnesium ions, refining bittern uses as alkaline raw material.The magnesium hydrate precipitate that ammonia process reaction removes the generation of magnesium ion process is sold as magnesium hydroxide products after being separated drying.
Owing to have employed technique scheme, the invention has the beneficial effects as follows:
1, by being removed by the calcium ions and magnesium ions in bittern with ammonia and volatile salt, refining bittern can substitute solid crude salt and use as alkaline raw material.
2, the magnesium hydrate precipitate produced in primary purification process can obtain highly purified magnesium hydroxide products after being separated, and the calcium magnesium precipitate produced in secondary refining process can obtain ca and mg fertilizer product after being separated, and can produce good economic benefit.
3, the sodium ion in bittern and calcium ions and magnesium ions obtain effective utilization, have given full play to the effect of recycling economy.
The present invention passes through comprehensive utilization of resources, be directly used in soda manufacture after saturated bittern can being refined, bittern produces salt amount increases by more than 15%, salt pan output increase about more than 50%, also effectively make use of the compositions such as the calcium ions and magnesium ions in bittern simultaneously, give full play to the advantage of recycling economy.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
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 to be evaporated, obtain the dense bittern that concentration is 22 degree Beaume;
Add solid salt in S2, the dense bittern that obtains to step S1, after changing salt, obtain saturated bittern;
S3, the saturated bittern obtained by step S2 enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 60 DEG C, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilizes 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 carries out drying, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern obtained by step S3 enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and with bittern slurries in obtaining, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixed gas, and wherein the volume ratio of carbonic acid gas is 38%; In described, add solid powder salt with bittern slurries, then clarify, filter to isolate calcium magnesium salts, obtain filtrate simultaneously and refine ammonia bittern, the calcium magnesium salts filtered to isolate is washed, and solid carries out drying 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 obtained by step S4 utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda manufacture 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 being separated.
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 to be evaporated, obtain the dense bittern that concentration is 23 degree Beaume;
Add solid salt in S2, the dense bittern that obtains to step S1, after changing salt, obtain saturated bittern;
S3, the saturated bittern obtained by step S2 enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 80 DEG C, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilizes 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 carries out drying, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern obtained by step S3 enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and with bittern slurries in obtaining, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixed gas, and wherein the volume ratio of carbonic acid gas is 40%; In described, add solid powder salt with bittern slurries, then clarify, filter to isolate calcium magnesium salts, obtain filtrate simultaneously and refine ammonia bittern, the calcium magnesium salts filtered to isolate is washed, and solid carries out drying 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 obtained by step S4 utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda manufacture 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 being separated.
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 to be evaporated, obtain the dense bittern that concentration is 23 degree Beaume;
Add solid salt in S2, the dense bittern that obtains to step S1, after changing salt, obtain saturated bittern;
S3, the saturated bittern obtained by step S2 enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, maintain 70 DEG C, obtain ammonia bittern slurries, described ammonia bittern slurries are clarified, utilizes 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 carries out drying, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash;
S4, the ammonia bittern obtained by step S3 enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, and with bittern slurries in obtaining, the carbon dioxide containing gas of use is carbonic acid gas and nitrogen mixed gas, and wherein the volume ratio of carbonic acid gas is 39%; In described, add solid powder salt with bittern slurries, then clarify, filter to isolate calcium magnesium salts, obtain filtrate simultaneously and refine ammonia bittern, the calcium magnesium salts filtered to isolate is washed, and solid carries out drying 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 obtained by step S4 utilize ammonia-soda process soda ash, technique is: by refining ammonia bittern in the carbonating tower of pump delivery solvay soda process soda manufacture 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 being separated.
Embodiment 4
Bittern again shines evaporation through Cemented filling to answering in threshing ground by carrying after halogen pump is extracted out, bittern concentration enrichment to 22 degree Beaume, after saturated, add the mixing of solid salt, bittern is delivered to after soda manufacture device district internalization salt through pipeline and refines, obtain saturated bittern, then after twice refining removing calcium ions and magnesium ions, be sent to carbonation process alkaline and use.The precipitation produced in treating process is respectively used to produce the product such as magnesium hydroxide, ca and mg fertilizer.Concrete technology flow process is described below:
Add salt through multiple solarization close to saturated bittern, make saturated bittern after changing salt and be delivered in de-magging tower and carry out with the ammonia of carbon dioxide removal in soda manufacture process reacting that (reaction equation is: Mg
2++ 2NH
4oH=Mg (OH)
2↓+2NH
4+), after the magnesium ion of removing 85-95%, then be delivered in carbonating tower and 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 being separated drying.The calcium magnesium precipitate produced in secondary refining process is sold as ca and mg fertilizer product.
Material balance
With embodiment 3, produce design in 8000 hours by application man-year, company answers that threshing ground is per hour can produce 62.50m
323 degree Beaume close to saturated bittern, multiple shine after bittern again and 400m
3/ h is 462.5m without flow after the bittern mixing of multiple solarization
3/ h, going of mixing bittern salt uses.Through accounting, liquid salt 320,000 tons can be used year, 4.16 ten thousand tons, coproduct hydrogen magnesium oxide.
Economic and Efficiency Analysis
Through accounting, use salt deduction refining expense and the equipment amortization working cost etc. brought in every side's mixing bittern can produce the economic benefit of 7.31 yuan, it is 2703.49 ten thousand yuan that year produces economic benefit.
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 carries out Conservative estimation by 4000 yuan, magnesium hydroxide profit per ton is 2000 yuan, and it is 8,320 ten thousand yuan that year produces economic benefit, and this project estimates that producing overall economic efficiency adds 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
Produce design in 8000 hours by application man-year, company answers that threshing ground is per hour can produce 62.50m
3bittern, close to saturated bittern, is then used conventional methods alkaline by 23 degree Beaume: with milk of lime, (effective constituent is Ca (OH)
2) removing crude brine in magnesium ion, then with soda ash removing crude brine in calcium ion.
Year produces Economic and Efficiency Analysis
Comparative example 2
Produce design in 8000 hours by application man-year, company answers that threshing ground is per hour can produce 62.50m
3bittern, close to saturated bittern, is then used conventional methods alkaline by 23 degree Beaume: lime ammonium carbonate method is with the magnesium ion in milk of lime removing crude brine.Then with the calcium ion in volatile salt removing crude brine.
Year produces Economic and Efficiency Analysis
Obviously can see with the economic benefit calculation table of comparative example 2 from embodiment 3, comparative example 1, adopt the technical program to process subsurface brine, a year economic benefit can greatly be improved.
The present invention is not limited to above-mentioned embodiment, and all are based on technical conceive of the present invention, and done structural improvement, all falls among protection scope of the present invention.
Claims (6)
1. utilize subsurface brine directly to prepare a method for soda ash, it is characterized in that: step is as follows:
S1, subsurface brine to be evaporated, obtain the dense bittern that concentration is 22-23 degree Beaume;
Add solid salt in S2, the dense bittern that obtains to step S1, after changing salt, obtain saturated bittern;
S3, the saturated bittern obtained by step S2 enter suction ammonia reactor, pass into not carbonated ammonia simultaneously, obtain ammonia bittern slurries, are clarified by described ammonia bittern slurries, filter to isolate magnesium hydroxide solid, and obtain filtrate is ammonia bittern simultaneously;
S4, the ammonia bittern obtained by step S3 enter carbonization reactor, pass into carbon dioxide containing gas simultaneously, with bittern slurries in obtaining, solid powder salt is added with bittern slurries in described, then clarify, filter to isolate calcium magnesium salts, obtain filtrate simultaneously and refine ammonia bittern; Described carbon dioxide containing gas is carbonic acid gas and nitrogen mixed gas, and wherein the volume ratio of carbonic acid gas is 38%-40%;
S5, the refining ammonia bittern obtained by step S4 utilize ammonia-soda process soda ash.
2. a kind of method utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, is characterized in that: in described step S3, inhales temperature in ammonia reactor and maintains 60-80 DEG C.
3. a kind of method utilizing subsurface brine directly to prepare soda ash as claimed in claim 1, is characterized in that: in described step S3, utilizes press filtration mode to filter to isolate magnesium hydroxide solid.
4. a kind of method 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 carries out drying, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
5. a kind of method 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 filtered to isolate is washed, and solid carries out drying and obtains ca and mg fertilizer and pack, and wash water is delivered to step S5 and carries out ammonia-soda process soda ash.
6. a kind of method 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 through pump delivery in the carbonating tower of solvay soda process soda manufacture technique, with the crystallization of carbon dioxide gas precursor reactant Formed acid hydrogen sodium, sodium bicarbonate again through high-temperature calcination in calcining furnace, obtains soda ash product after being separated.
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| 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 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1023913A (en) * | 1963-03-13 | 1966-03-30 | Solvay | An improved process for the manufacture of sodium carbonate |
| CN1047268A (en) * | 1989-05-16 | 1990-11-28 | 山东省东阿县化工技术开发公司 | A kind of method of utilizing bittern to prepare soda ash |
| CN101289200A (en) * | 2007-04-16 | 2008-10-22 | 中国盐业总公司 | Technological process for purifying bittern |
| CN101712481A (en) * | 2009-12-08 | 2010-05-26 | 耿世达 | Method for preparing high-purity lithium carbonate and other available byproducts from salt lake brine |
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| JPS5015797A (en) * | 1973-06-15 | 1975-02-19 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1023913A (en) * | 1963-03-13 | 1966-03-30 | Solvay | An improved process for the manufacture of sodium carbonate |
| CN1047268A (en) * | 1989-05-16 | 1990-11-28 | 山东省东阿县化工技术开发公司 | A kind of method of utilizing bittern to prepare soda ash |
| CN101289200A (en) * | 2007-04-16 | 2008-10-22 | 中国盐业总公司 | Technological process for purifying bittern |
| CN101712481A (en) * | 2009-12-08 | 2010-05-26 | 耿世达 | Method for preparing high-purity lithium carbonate and other available byproducts from salt lake brine |
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