CN102205979A - Salt, alkali and calcium combined cycle production technology by the use of well mineral salt - Google Patents
Salt, alkali and calcium combined cycle production technology by the use of well mineral salt Download PDFInfo
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Abstract
The invention relates to a salt, alkali and calcium combined cycle production technology by the use of well mineral salt. Based on the exploitation of brine from well mineral salt, the salt, alkali and calcium combined cycle production technology by the use of well mineral salt is a cycle production technology, which focuses on the technology for making alkali from brine by the ammonia-soda process and takes account of the vacuum salt-making (including the brine refinement) and calcium-making technologies. Alkali-making wastewater replaces most fresh water to be injected into a salt mine well to collect brine, and the obtained high-calcium brine is taken as the raw material of the salt and calcium (including liquid calcium) co-production as well as the raw material for preparing alkali and other chemical production raw materials, wherein the liquid calcium can be used to produce liquid salt; alkali-making waste residues are injected into an underground dissolution cavern, namely a salt cavern which is formed by the exploitation of brine from well mineral salt, thus accomplishing the combined cycle production technology in which alkali-making and salt-making technologies are closely related with materials. The produced wastes are used as resources or undergo a harmless treatment, thus protecting the environment. In addition, the utilization rate of sodium chloride in rock salt reaches 100%, achieving maximum efficiency.
Description
Technical field
The present invention relates to utilize the combined cycle production technique of well mine salt as raw material production salt, alkali and optional calcium product.More particularly, the invention provides based on the well mine salt mining brine, based on solvay soda process bittern alkali-making process, take into account a kind of cycle production process of technologies such as vacuum salt production (Halogen crystal system), system calcium, wherein: replace fresh water with waste ammonia-soda solution, inject the salt mine down-hole to adopt halogen, obtain high calcium (containing liquid calcium) bittern, as the raw material of salt calcium coproduction and the raw material of preparation system alkali or other Chemical Manufacture raw material, wherein liquid calcium can be used for the production liquid salt; And the soda-manufacturing waste residue injection is adopted formed underground molten chamber of halogen or salt chamber by well mine salt; system alkali, salt producing craft and the big combined cycle production technology of material contact tightness degree have been realized; the refuse that produces gets utilization or harmless treatment; help protecting environment; the sodium-chlor utilization ratio reaches absolutely in the rock salt, realizes maximizing the benefits.
Background technology
Salt (NaCl) is the necessary article of common people's daily life, also is the basic material of chemical industries such as two alkali.The production of salt mainly is divided into sea salt and well mine salt, in recent years, because a large amount of sea salt beach resources is taken over for use the continuous atrophy of Salt production, and the fast development along with the continuous discovery of rock salt mining deposits of well mine salt industry, well mine salt accounts for the whole nation and produces the ratio of salt total amount near 50%.China's well mine salt production technology since the fifties in last century from external introduction, particularly in recent years, by introducing the external advanced salt producing craft of digestion, domestic salt making technology level is greatly improved, good reaches world-class levels substantially, but mean level (ML) has bigger gap with external advanced well mine salt manufacturing enterprise, domestic most of enterprise ubiquity production management level is low, energy consumption and production cost height, rock salt comprehensive utilization of resources rate is low etc., particularly: 1, the salt slurry of Chan Shenging, easily contaminate environment; 2, stay a large amount of underground salt chambeies after the Caused by Rock Salt Solution Mining, have geologic hidden peril.
Typical well mine salt production process as shown in Figure 1, it comprises: inject salt well extraction saturated bittern with fresh water, evaporation then (preferred vacuum-evaporation) obtains solid salt, and produces the salt slurry as waste material.This production technique can cause geologic hidden peril.
At present, part well mine salt enterprise has taked salt slurry to annotate the effective measure of well, protected environment, and the underground huge salt chamber that rock salt mining stays is not effectively addressed and utilizes.Abroad, the molten chamber of salt mine solution mining is mainly used in and stores oil, Sweet natural gas etc., more than 50 year history has been arranged, particularly in recent years, American-European developed country builds the solution mining solution cavity one after another in salt mine, be used for storing in a large number oil, Sweet natural gas, chemical gases, solid waste etc.Therefore, save energy and reduce the cost, reduce production costs, improve comprehensive utilization of resources efficient, and how to utilize underground salt chamber be the problem that China well mine salt enterprise need research and solve.
Soda industry is one of basic sector of chemical industry, is called as the mother of industry, occupies crucial status in national economy.World's soda ash production technique mainly contains ammonia alkali technology, integrated soda production and urao production technique, from world wide, uses many and the big chemosynthesis alkali-making process of industrial scale is solvay soda process.Typical solvay soda process alkali-making process process as shown in Figure 2.
(Ernest Solvay is a raw material with salt, ammonia, carbonic acid gas 1832-1922) to Belgian's Sol dimension in 1862, has made yellow soda ash.This process quilt is called solvay soda process (ammomia soda process), be also referred to as Solvay alkaline making process, so far have the history in over one hundred year, its technical maturity is reliable, the quality product excellence, and this technology need not supporting synthetic ammonia installation, it is short to have operational path, normal temperature and pressure is produced, and technological process control is convenient, single, the safe advantage such as reliable of operating safety.This reaction divided for three steps carried out:
NH
3+CO
2+H
2O→NH
4HCO
3
NH
4HCO
3+NaCl→NaHCO
3+NH
4Cl
2NaHCO
3→Na
2CO
3+CO
2+H
2O
The CO that reaction generates
2Can reclaim usefulness again, and NH
4Cl can react with unslaked lime again, produces NH
3, use as raw material again: 2NH
4Cl+CaO===2NH
3+ CaCl
2+ H
2O.
But the shortcoming that exists is: 1, solid salt system alkali, and the raw material salt utilization ratio is low, and only 70%, the production cost increase; 2, producing a large amount of slops, waste residues needs discharging, contaminate environment, and while calcium chloride etc. causes the waste of resource.Up to the present solvay liquor, waste residue utilization rate are lower, and general waste liquid all is to adopt outer discharge method, easy polluted source; Waste residue takes the stacking mode to handle, and the place demand is big, and waste land resources is dealt with Yi Yehui improperly and caused environmental pollution.Therefore, mostly the construction of ammonia alkali enterprise is by the sea or meagrely-populated uncultivated area in the world.Pressure along with environmental protection strengthens in recent years, and the application of solvay soda process and development are subjected to certain limitation and restriction.So it is the technical barrier that ammonia alkali enterprise develops in a healthy way and must face that slops, waste reside comprehensive utilization are handled.
During solvay soda process is produced, 1 ton of soda ash of every production will produce the waste residue (butt) of 300-350kg, mainly contain lime carbonate, magnesium hydroxide, calcium oxide etc., and ammonia alkali enterprise adopts to efflux the method processing waste residue of stacking or toppling over off-lying sea at present.And the every production of solvay soda process 1t soda ash can produce 8-10m
3Waste liquid, its roughly composition be: CaCl
295-115g/l; NaCl 50-51g/l.With regard to the waste ammonia-soda solution utilization was handled, present worldwide ammonia alkali enterprise adopted the mode of effluxing to handle, and at first takes measures to regulate the pH value of waste ammonia-soda solution that is:, reached externally discharging after the standard.Though also do not have calcium chloride in the waste ammonia-soda solution, sodium-chlor limit row index at present in the environmental protection standard, the higher waste ammonia-soda solution ground discharging of a large amount of saltiness still can impact environment, in addition, a large amount of NaCl, CaCl
2Deng falling with discharging of waste liquid is very unfortunate, has not only caused the wasting of resources, and does not meet the requirement of modern enterprise.Therefore, each ammonia alkali enterprise researchs and develops waste ammonia-soda solution one after another and utilizes technology in the world, and the present technology of having developed and being applied has:
One, waste ammonia-soda solution is through beach solar evaporation moisture, and most of NaCl is separated out by crystallization, will shine the back mother liquor more again and move on to indoor heating evaporation, and the control water yield, insulation separate, crystallisation by cooling, produce calcium tablet (CaCl22H2O).Come to this as the part waste liquid of Lianyun Harbour alkali factory and to handle, earlier in the beach solar evaporation salt manufacturing of saltern, the Taibei, the mother liquor after the salt manufacturing is sold to system calcium factory, and calcium tablet is produced in regeneration.
Two, waste ammonia-soda solution is through beach solar evaporation moisture content, when NaCl when saturated, adopt the vacuum salt production method, after indoor heating evaporation salt manufacturing, produce calcium tablet for system calcium operation again.Adopt this operational path Shandong calcium chloride factory of seaization stock company at present, production capacity has reached 450,000 tons of calcium tablets.
Three, waste ammonia-soda solution directly adopts the vacuum salt production method, after indoor heating evaporation salt manufacturing, produces calcium tablet for system calcium operation again.Adopting this operational path is Qingdao alkali industry, Tianjin Caustic Soda Plant etc., but deficiency in economic performance.
Owing to need the waste ammonia-soda solution enormous amount of processing, add the restriction of envrionment conditions, and the restriction of processing and utilizing cost, therefore, though above-mentioned technology obtains certain application, processing and utilizing waste ammonia-soda solution comparatively small amt, most of waste ammonia-soda solution still is discharged.
In this year, the waste residue that people's special concern is produced in ammonia alkali technology, the processing of waste liquid utilize waste residue, waste liquid to reduce the stacking of waste residue and the discharging of minimizing waste liquid by adopting the whole bag of tricks.
Chinese patent application 00134381 (CN1297847A) discloses a kind of waste ammonia-soda solution and contains sodium sulfate waste liquid comprehensive utilization method, separation with the water-insoluble in the alkali wasteliquid after, the waste liquid of waste ammonia-soda solution and contains sodium sulfate is reacted, generate gypsum and sodium chloride solution, isolate gypsum deposition, add the soda ash reaction again, separate the light calcium carbonate precipitation that generates and obtain light calcium carbonate product, remaining is main component with sodium-chlor, a small amount of superfluous soda ash, the light salt brine of micro-calcium ion and sulfuric acid acid ion, return in the alkali producing process as system alkali raw material, with two kinds of waste liquid treatment of wastes with processes of wastes against one anothers, by-product gypsum and light calcium carbonate product, both administer waste liquid, reclaimed resource again, saved the energy.
Chinese patent application 200510136331 (CN1814548A) discloses a kind of no waste emission ammonia-sode process anhydrous sodium carbonate process, it is that the waste residue liquid that ammonia still process comes out is handled, and it is characterized in that: waste residue liquid (6) through separation circuit (7) separate slagging-off and through wash engineering major product (8); Supernatant liquor (9) in reaction process (10) with freeze nitre (Na2SO4) react refined plaster product (12); The circulation fluid (13) that reaction process (10) comes out enters salt solution operation (2) and recycles; Unnecessary circulation fluid enters salt manufacturing operation (14) and produces refined salt product (15).50%NaCl is reclaimed in the recycle of this invention waste residue liquid approximately, and the salt refining expense can be saved more than 50%, can the about 10m of saving salt fresh water
3/ T alkali.
The open method of Chinese patent application 200710139304 (CN101125673A) by ammonia-soda process waste liquid direct production calcium chloride.
Can obtain from top introduction: 1, the production technique of soda factory and well mine salt enterprise is separate, and material and energy flow process do not interrelate, and establish one's own system, and resource utilization is low, and two kinds of production technology advantages can not get bringing into play fully; 2, this two production technique all will produce negative benefit, that is: soda factory can produce a large amount of liquid and waste slag producedly, and well mine salt production can stay the underground salt of a large amount of depleted chamber, exists big environmental protection and geologic hidden peril, and, can't solve these difficult problems alone by they self condition.
The applicant (Jiangsu JingShen Salt and Electrical Machinery Plant, preceding title for applicant company, existing name is called: Chinese patent application 200910183644 (CN101629484A) the refreshing salinization of Jiangsu well stock company) discloses a kind of waste ammonia-soda solution and has been used for the resource utilization method that sodium sulfate type salt mine notes well is adopted halogen, waste ammonia-soda solution is direct, or after in waste ammonia-soda solution, adding fresh water, substitute fresh water and inject the salt mine down-hole, dissolving rock salt forms ore deposit halogen, after natural subsidence, exploitation ore removal halogen.This invention is used for the sodium sulfate type salt mine with waste ammonia-soda solution and adopts halogen, utilizes waste ammonia-soda solution to contain CaCl
2With the characteristics of sodium sulfate type salt mine, with waste ammonia-soda solution directly or convert and inject the salt mine down-hole behind the water and adopt halogen, obtain the low high-quality bittern of sodium sulphate content, both reduced the sodium sulphate content in the bittern, reclaimed NaCl and the CaCl in the waste ammonia-soda solution again
2, waste ammonia-soda solution has obtained recycling, has reduced the discharging of refuse.Prepared brine can be used for vacuum salt production, bittern system alkali, ore deposit halogen day solar salt shan and other chemical industry.But, sulfate radical in the technology of this method removes, the calcium sulfate precipitation process is all finished in underground mine, because the subsurface picture complexity, the grade difference of rock salt is big, and the brine quality after the exploitation is difficult to be guaranteed, exploit efficient low, suitability for industrialized production is difficult to realize, therefore, is controlling the raw brine quality, still remain further to be optimized on suitability for industrialized production realizes easily, the efficient needs of bittern exploitation further improve.
Goal of the invention
In order to solve the problems of the technologies described above, satisfy the development salt chemical engineering, prolong the needs of industrial chain, the present inventor is on the basis of research solvay soda process production technique and well mine salt production technique, making full use of needs underground dissolved salt mining of fresh water and mining back to produce the characteristics in the molten chamber of underground salt in well mine salt production, in the bittern system of realization alkali, the waste liquid that utilizes soda ash production to produce replaces fresh water notes well to adopt halogen, obtain high calcium brine, be used for the coproduction of salt calcium, sodium-chlor and calcium chloride obtain reclaiming, and have improved resource utilization; And the waste residue that system alkali produces after treatment, inject discarded or be about to and store in the underground salt of the depleted chamber, the difficult problem of the liquid and waste slag produced processing that has successfully solved soda ash production and produced, effectively prevent from simultaneously to realize just salt manufacturing on meaning and system (pure) alkali combined cycle Technology because of there is the geologic hidden peril that produces in underground salt chamber.
Description of drawings
Fig. 1: typical well mine salt production process.
Fig. 2: typical solvay soda process alkali-making process process.
Fig. 3: be applicable to the salt, alkali of sodium sulfate type well mine salt and the combined cycle technological process of production sketch of optional calcium.Illustrate: the output of liquid calcium, solid calcium and liquid salt, can determine and regulate according to the produce market situation; Low nitre halogen output under the prerequisite that satisfies system alkali needs, can be determined and regulates according to enterprise and market bittern demand; The bittern denitration is the example explanation with the ground denitrating technique, but also available underground denitrating technique.
Fig. 4: be applicable to the salt, alkali of calcium sulfate type well mine salt and the combined cycle technological process of production sketch of optional calcium.Illustrate: the output of liquid calcium, solid calcium, can determine and regulate according to the produce market situation.
Summary of the invention
The present inventor has carried out the analysis and research of science to ammonia alkali production technology and well mine salt production technology, utilize common salt mine to be the characteristics of sodium sulfate type salt mine, give full play to the advantage of these two kinds of technologies, the saline and alkaline calcium combined cycle production technology (seeing Fig. 3) that ammonia-soda process combines with well mine salt production has been proposed, this technology is as the basis take the well mine salt exploitation, take ammonia alkali technology as main body, auxiliary salt manufacturing (comprising brine refining) and calcium technology processed. At first use the ammonia alkali technology of alkali making from brine, realize saving energy and reduce the cost, reduce production costs; Utilize then waste ammonia-soda solution to replace fresh water, inject the salt mine down-hole and adopt halogen, (calcium chloride content is higher and bittern that sodium chloride is saturated to obtain high calcium brine, together lower) after, next two process routes are arranged: one is to use vacuum evaporating crystalization technology, realizes salt, calcium coproduction, obtains two kinds of solid products that meet national standard of sodium chloride and calcium chloride dihydrate, according to market demand, this technology also can be produced liquid calcium (calcium chloride content at 22-43wt% and sodium chloride is saturated) product; Other one is to use CaCl2With Na after the dissolving2SO
4Reaction generates CaSO4The mechanism of precipitation, (sodium sulphate content is higher and bittern that sodium chloride is saturated with high calcium brine and high caldo by a certain percentage, together lower) mix, to reduce the content of sulfate ion in the bittern, make with extra care and obtain low caldo, be used for alkali making from brine, vacuum salt production or ore deposit halogen day solar salt etc. to less demanding other chemical industry of ammonia content, use low caldo to be conducive to the energy-saving and cost-reducing of these enterprises, like this CaCl in the waste ammonia-soda solution2Obtained sufficient recycling with NaCl, the utilization rate of sodium chloride reaches absolutely in the exploitation rock salt. And the alkaline residue that ammonia alkali produces (contains the salt slurry that alkaline salt manufacturing produces, lower with) inject rock salt and adopt formed molten chamber after the halogen, carry out underground storage and stack, thereby solve the difficult problem that alkaline residue is processed, when the Underground Salt chamber is effectively used, can also effectively suppress the generation of geological disaster. Therefore, this technology successfully organically combines ammonia-soda process alkaline and well mine salt production, the characteristics of utilizing well mine salt to produce, successfully solved the difficult problem of liquid and waste slag produced processing during ammonia alkali is produced, effectively prevent from simultaneously having the geologic hidden peril that produces because of the Underground Salt chamber, so that two process advantages are not fully exerted, realized salt truly, alkali (with optional calcium product) circulation Joint Production, both energy-saving and cost-reducing, reduce production costs, reduced again the discharging of refuse, rock salt comprehensive utilization of resources rate is maximized, be conducive to environmental protection, realized the purpose of recycling industries and clean production.
In addition, through research, saline and alkaline calcium combined cycle production technique also is applicable to the production (see figure 4) of calcium sulfate type well mine salt.At first use the ammonia alkali technology of bittern system alkali, realize saving energy and reduce the cost, reduce production costs; Utilize waste ammonia-soda solution to replace fresh water then, inject the salt mine down-hole and adopt halogen, after obtaining high calcium brine, utilization vacuum evaporating crystalization technology, realize the coproduction of salt calcium, obtain two kinds of solid phase prods that meet national standard of sodium-chlor and Calcium dichloride dihydrate, according to market demand, this technology also can be produced liquid calcium (calcium chloride content at 22-43wt% and sodium-chlor is saturated) product, CaCl in the waste ammonia-soda solution like this
2Obtained sufficient recycling with NaCl, the utilization ratio of sodium-chlor reaches absolutely in the exploitation rock salt; And the alkaline residue that ammonia alkali produces injects rock salt and adopts formed molten chamber after the halogen, carries out underground storage to stack, thereby solves the difficult problem that alkaline residue is handled, and when underground salt chamber is effectively used, can also suppress the generation of geologic hazard effectively.Compare with the saline and alkaline calcium combined cycle production technique that applies to the sodium sulfate type well mine salt, technical process is simplified, and target product is less, but the basic technology route is identical.
That is to say, the present inventor has carried out analysis of science research to excellent, the shortcoming of ammonia alkali production technique and well mine salt production technique, making full use of on the advantage basis of two kinds of production technique, proposing the saline and alkaline calcium combined cycle production technique that solvay soda process combines with well mine salt production.This technology is based on the well mine salt exploitation, and based on ammonia alkali technology, technologies such as assisted vacuum salt manufacturing (comprising brine refining), system calcium realize system alkali, salt producing craft and the big combined cycle production technology of material contact tightness degree.
For sodium sulfate type salt rock salt: the ammonia alkali technology of at first using bittern system alkali, utilize waste ammonia-soda solution to replace fresh water then, inject the salt mine down-hole and adopt halogen, after obtaining high calcium brine, utilization vacuum evaporating crystalization technology realizes the coproduction of salt calcium, obtains two kinds of solid phase prods that meet national standard of sodium-chlor and Calcium dichloride dihydrate, according to market demand, this technology also can be produced liquid calcium (calcium chloride content at 22-43wt% and sodium-chlor is saturated) product; If well mine salt is a sodium sulfate type, the high calcium brine that obtains so also can use CaCl
2With dissolving back Na
2SO
4Reaction generates CaSO
4Sedimentary mechanism, by a certain percentage high calcium brine is mixed with high caldo, obtain hanging down caldo to reduce the content of sulfate ion in the bittern, to make with extra care, be used for bittern system alkali, vacuum salt production or ore deposit halogen day solar salt shan etc. to less demanding other chemical industry of ammonia content, like this CaCl in the waste ammonia-soda solution
2Obtained sufficient recycling with NaCl.And the alkaline residue that ammonia alkali produces injects rock salt and adopts formed molten chamber after the halogen, carries out underground storage to stack, thereby solves the difficult problem that alkaline residue is handled, and when underground salt chamber is effectively used, can also suppress the generation of geologic hazard effectively.
For calcium sulfate type well mine salt: at first use the ammonia alkali technology of bittern system alkali, realize energy-saving and cost-reducingly, reduce production costs; Utilize waste ammonia-soda solution to replace fresh water then, inject the salt mine down-hole and adopt halogen, after obtaining high calcium brine, utilization vacuum evaporating crystalization technology, realize the coproduction of salt calcium, obtain two kinds of solid phase prods that meet national standard of sodium-chlor and Calcium dichloride dihydrate, according to market demand, this technology also can be produced liquid calcium (calcium chloride content at 22-43wt% and sodium-chlor is saturated) product, CaCl in the waste ammonia-soda solution like this
2Obtained sufficient recycling with NaCl; Equally, the alkaline residue that ammonia alkali produces injects rock salt and adopts formed molten chamber after the halogen, carries out underground storage and stacks, thereby solve the difficult problem that alkaline residue is handled, and when underground salt chamber is effectively used, can also suppress the generation of geologic hazard effectively.
Therefore, this technology successfully organically combines ammonia alkali legal system alkali and well mine salt production, the characteristics of utilizing well mine salt to produce, successfully solved the difficult problem of liquid and waste slag produced processing during ammonia alkali is produced, effectively prevent from simultaneously to have the geologic hidden peril that produces because of underground salt chamber, make two process advantages be not fully exerted, realized salt truly, alkali (with optional calcium product) circulation combination producing, both energy-saving and cost-reducing, reduce production costs, reduced the discharging of refuse again, rock salt comprehensive utilization of resources rate is maximized, help environmental protection, realized the purpose of recycling industries and clean production.
According to the present invention, basic principle of work is: saline and alkaline calcium combined cycle production technique is based on the well mine salt exploitation, based on ammonia alkali technology, assisted vacuum salt manufacturing (containing liquid salt), technologies such as system calcium, its core solves a solvay liquor recycling and a soda-manufacturing waste residue innoxious process for treating difficult problem exactly, at first utilize well mine salt to need fresh water to annotate well and adopt halogen reality, replace fresh water with solvay liquor, inject the salt mine down-hole and adopt halogen, after obtaining high calcium brine, utilization vacuum evaporating crystalization technology realizes the coproduction of salt calcium, obtain solid sodium chloride, solid Calcium dichloride dihydrate and liquid calcium product, CaCl in the waste ammonia-soda solution like this
2Having obtained sufficient resource utilization with NaCl recycles.And the waste residue that system alkali produces injects rock salt and adopts formed molten chamber after the halogen, carrying out underground storage stacks, thereby realized the difficult problem of alkaline residue harmless treatment, when underground salt chamber is effectively used, can also suppress the generation of geologic hazard effectively, therefore, realize closely big combined cycle production technology of system alkali, the contact of salt producing craft material.When the sodium sulfate type well mine salt uses saline and alkaline calcium combined cycle production technique, also use CaCl
2With dissolving back Na
2SO
4Reaction generates CaSO
4Sedimentary mechanism, by a certain percentage high calcium brine or liquid calcium are mixed with high caldo, to reduce the content of sulfate ion in the bittern, improve the quality of bittern, refining low caldo and the liquid salt product of obtaining, be used for chemical industry such as bittern system alkali, vacuum salt production or ore deposit halogen day solar salt shan, enlarged operational path and selected face.
The working process brief introduction of the technology of two kinds of dissimilar well mine salts of employing of the present invention:
1, be applicable to the saline and alkaline calcium combined cycle production technique working process brief introduction (see figure 3) of sodium sulfate type well mine salt: this technology is at first used the ammonia alkali technology of bittern system alkali, realizes saving energy and reduce the cost, and reduces production costs; Utilize waste ammonia-soda solution to replace fresh water then, inject the salt mine down-hole and adopt halogen, after obtaining high calcium brine, two operational paths are arranged: one is utilization vacuum evaporating crystalization technology, realize the coproduction of salt calcium, obtain two kinds of solid phase prods that meet national standard of sodium-chlor and Calcium dichloride dihydrate, according to market demand, this technology also can be produced the liquid calcium product; Other one is utilization CaCl
2With dissolving back Na
2SO
4Reaction generates CaSO
4Sedimentary mechanism, by a certain percentage high calcium brine is mixed with high caldo, to reduce the content of sulfate ion in the bittern, make with extra care and obtain low caldo, be used for bittern system alkali, vacuum salt production or ore deposit halogen day solar salt shan etc. to less demanding other chemical industry of ammonia content, use low caldo to help the energy-saving and cost-reducing of these enterprises, this two operational path can both make CaCl in the waste ammonia-soda solution
2Obtained sufficient recycling with NaCl.And the alkaline residue that ammonia alkali produces injects rock salt and adopts formed molten chamber after the halogen, carries out underground storage to stack, thereby solves the difficult problem that alkaline residue is handled, and when underground salt chamber is effectively used, can also suppress the generation of geologic hazard effectively.
2, be applicable to the saline and alkaline calcium combined cycle production technique working process brief introduction (see figure 4) of calcium sulfate type well mine salt: at first use the ammonia alkali technology of bittern system alkali, realize saving energy and reduce the cost, reduce production costs; Utilize waste ammonia-soda solution to replace fresh water then, inject the salt mine down-hole and adopt halogen, obtain high calcium brine after, utilization vacuum evaporating crystalization technology realizes the coproduction of salt calcium, obtains sodium-chlor and Calcium dichloride dihydrate solid phase prod, according to market demand, this technology also can be produced liquid calcium, like this CaCl in the waste ammonia-soda solution
2Obtained sufficient recycling with NaCl; And the alkaline residue that ammonia alkali produces injects rock salt and adopts formed molten chamber after the halogen, carries out underground storage to stack, thereby solves the difficult problem that alkaline residue is handled.
In the present invention and more particularly shown in Fig. 1 "
Saturated bittern" be saturated salt (sodium-chlor) water on the ordinary meaning, other the foreign matter content＜2wt% except that sodium-chlor, preferred＜1wt%, more preferably＜0.5wt%, most preferably＜0.2wt%.This common bittern can be used in the system alkali step of the present invention.
Therefore, in first embodiment of the present invention, provide:
1, the combined cycle production technique of a kind of salt that utilizes the sodium sulfate type well mine salt, alkali and optional calcium product, it may further comprise the steps:
1), utilize solvay soda process to prepare alkali (Na with bittern
2CO
3), obtain solid sodium carbonate, produce waste ammonia-soda solution (abbreviation waste liquid) and ammonia alkali waste residue (abbreviation waste residue) simultaneously,
2), the waste liquid of above step replaces fresh water to be injected into sodium sulfate type salt mine down-hole adopting halogen, obtain high calcium brine; Simultaneously stayed molten chamber underground, i.e. salt chamber,
3), above step 2) high calcium brine carry out vacuum-evaporation, cause crystallization, obtain solid sodium chloride and Calcium dichloride dihydrate and optional liquid calcium product, and/or
3 '), above step 2) high calcium brine and high caldo according to certain mixed, form calcium sulfate precipitation, remove the calcium sulfate precipitation thing, obtain low caldo and
4), waste residue that above step 1) is produced is infused in step 2) formed underground salt chamber, or inject other and annotate well with fresh water usually and adopt left salt chamber after the halogen.
2, according to above 1 technology, wherein step 3 ') low caldo return in the step 1) bittern of using as system alkali, perhaps be used for common vacuum salt or ore deposit halogen day solar salt shan.
3,, also be included in step 4) following steps 5 afterwards according to above 1 technology):
The liquid calcium product of above step 3) and high caldo form calcium sulfate precipitation and obtain liquid salt (NaCl) product according to certain mixed.
4, according to above 1 or 3 technology, wherein high caldo is adopted halogen and is obtained by fresh water being injected sodium sulfate type salt mine down-hole, simultaneously in the underground salt chamber that stayed.
5, according to any one described technology among the above 1-4, wherein said salt chamber is the salt chamber that the salt mine has been stayed after the rational exploitation, or discarded salt chamber.Described " discarded salt chamber " be meant from the geology security consideration, after exploitation, reach the rock salt mining rate of national regulation after, do not allowed to continue to exploit and the underground salt chamber that stays.
6, according to above 1 technology, wherein the bittern of step 1) is low caldo or saturated bittern or both combinations, preferably low nitre and the saturated bittern of sodium-chlor.
More than in 1 " step 3) and/or 3 ') " represent that these two steps can carry out or promptly carry out respectively side by side simultaneously, that is to say, more than method in 1 comprise step 1), 2), 3) and 4), perhaps comprise step 1), 2), 3 ') and 4), perhaps comprise step 1), 2), 3) and 3 ') and 4).
Above and below, described " discarded salt chamber " be meant from the geology security consideration, after exploitation, reach the rock salt mining rate of national regulation after, do not allowed to continue to exploit and the underground salt chamber abandoned.This is that those skilled in the art know.
With following described, because underground rock salt component content is extremely inhomogeneous, add that the subsurface geology situation is complicated according to here, the ore deposit alkali quantitative changeization of exploitation is big, "
The sodium sulfate type well mine salt" composition of composition of 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 is generally at＞12g/l-30g/l, preferred 12.5-27g/l, more preferably 17-25g/l, more preferably 19-24g/l, most preferably 20-23g/l scope (for example about 22g/l) again, 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 "."
Calcium sulfate type well mine salt" composition of composition of 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 preferably 1.5-4g/l, most preferably 1.6-3g/l scope (for example about 2.6g/l) again; CaSO
4Content is generally at 3-8g/l, preferred 3.5-7.2g/l, more preferably 4-6.8g/l, more preferably 4.5-6.3g/l, most preferably 5.0-6.0g/l (for example about 5.5g/l) again.
With following described, the production factor that fresh water is adopted halogen generally is 60-90% according to here, preferred 70-86%, more preferably 75-83% most preferably is approximately 80%, considers that the present invention is that solvay liquor replaces fresh water to adopt halogen, its most preferably production factor be approximately 86%.
According to here with following described, "
Low caldo" be meant Na
2SO
4Content is at 0.1-12g/l, preferred 1-10g/l, more preferably 2-8g/l, more preferably 4-8g/l again, most preferably 5-7g/l scope (for example about 6g/l) and NaCl content is at 100-330g/l, preferred 200-320g/l, more preferably 230-315g/l, most preferably a kind of bittern of 270-312g/l scope (for example about 310g/l).Preferably above step 3 ') the low caldo that obtains.
According to here with following described, "
High calcium brine (being called for short high calcium halogen)" be meant CaCl
2Content is at 30-120g/l, preferred 40-115g/l, more preferably 50-110g/l, more preferably 60-100g/l again, most preferably 70-95g/l scope (for example 90g/l) and NaCl content are at 100-250g/l, preferred 150-240g/l, more preferably 170-235g/l, more preferably 180-232g/l again, most preferably 190-232g/l scope (for example about 230g/l) a kind of bittern.
So according to the above, in general, " high nitre " bittern refers to Na in the present invention
2SO
4Content is generally at the bittern (being NaCl water) of＞12g/l-30g/l scope." high calcium " is meant CaCl
2Content is at the bittern (being NaCl water) of 30-120g/l." low nitre " bittern is meant Na
2SO
4Content is at the bittern (being NaCl water) of 0.1-12g/l.The preferable case of these terms referring to above for Na
2SO
4Or CaCl
2The described preferable case of content.The explanation here also is applicable to first and second embodiment of the present invention.
Composition is inequality in the waste ammonia-soda solution that each ammonia alkali enterprise produces.In the present invention, based on the soda ash output of 600,000 t/, the waste ammonia-soda solution amount generally is 6.5-11.5m
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, 290-325kg/t soda ash especially, for example about 320kg/t soda ash (butt)." t " expression " ton ".
The quality of liquid calcium product is in the present invention: calcium chloride content is generally 250-290g/l, preferred 260-280g/l, more preferably 265-275g/l, for example about 270g/l; NaCl content is generally 85-145g/l, preferred 100-130g/l, more preferably 105-125g/l, for example about 110g/l.
Second embodiment according to the present invention provides:
7, utilize the combined cycle production technique of salt, alkali and the optional calcium product of calcium sulfate type well mine salt, it may further comprise the steps:
1), utilize solvay soda process to prepare alkali (Na with bittern
2CO
3), obtain solid sodium carbonate, produce waste ammonia-soda solution and ammonia alkali waste residue simultaneously,
2), the waste liquid of above step replaces fresh water to be injected into calcium sulfate type salt mine down-hole adopting halogen, obtain high calcium brine, simultaneously in the underground salt chamber that stayed,
3), above step 2) high calcium brine carry out vacuum-evaporation, cause crystallization, obtain solid sodium chloride and Calcium dichloride dihydrate and optional liquid calcium product,
4), waste residue that above step 1) is produced is infused in step 2) formed underground salt chamber, or inject other and common adopt formed salt chamber after the halogen with fresh water.
8, according to above 7 described technologies, wherein said salt chamber is the salt chamber that the salt mine has been stayed after the rational exploitation, or discarded salt chamber.Described " discarded salt chamber " be meant from the geology security consideration, after exploitation, reach the rock salt mining rate of national regulation after, do not allowed to continue to exploit and the underground salt chamber that stays.
9, according to above 7 technology, wherein the bittern of step 1) is to be injected into calcium sulfate type salt mine down-hole with fresh water to adopt halogen, the bittern that obtains.
Expressing phrase " liquid calcium product and high caldo are according to certain mixed " is meant, form the principle of calcium sulfate precipitation thing according to calcium ion and sulfate radical, from the liquid calcium that content calculated of the sulfate radical of the content of the calcium ion of liquid calcium product and high caldo and the part by weight of high caldo consumption.The actual ratio of using can the usage ratio of calculating ± 5% range.
In embodiments of the invention, the gordian technique that is involved mainly is: (1) salt manufacturing (Halogen crystal system), alkali-making process organically combine, and realize the closed systemic circulation of material flow; (2) solvay liquor substitutes fresh water and annotates the technology that well is adopted halogen; (3) process for refining of ore deposit halogen; (4) soda-manufacturing waste residue is annotated the technology that well stores.
The innovation part is: ammonia alkali legal system alkali and well mine salt production are combined, salt truly, alkali (with optional calcium) circulation combination producing have been realized, material flow has formed systemic circulation, both energy-saving and cost-reducing, reduce production costs, reduced the discharging of refuse again, sodium-chlor and calcium chloride are reclaimed fully, and the utilization ratio of sodium-chlor reaches absolutely in the exploitation rock salt; Simultaneously effectively prevent geologic hidden peril, rock salt comprehensive utilization of resources rate is maximized, helps environmental protection, has realized the purpose of recycling industries and clean production.
" choose " expression in this application wantonly and be with or without two kinds of situations, or under two kinds of situations of representing to carry out or do not carry out.
The quality of soda ash, solid salt, solid calcium and liquid salt is with reference to national standard in example of the present invention.
The major advantage of invention:
1, salt, alkali and optional calcium are realized combined cycle production truly, technology is reasonable, material flow connects each other, and formed the closed circulation of big material, and energy-saving and cost-reducing, reduce production costs safety and environmental protection, reached the recycling industries and clean production effect, the maximization of economic benefit.
2, waste recycling realizes two-way treatment, prevents that effectively negative benefit from producing.Soda-manufacturing waste residue obtains underground buried harmless treatment on the one hand, and environmental protection and economy can also reduce the risk that geologic hazard produces; Sodium-chlor in the solvay liquor and calcium chloride obtain resource utilization and recycle on the other hand, turn waste into wealth, and the utilization ratio of sodium-chlor reaches absolutely in the exploitation rock salt, in the protection environment, improves well mine salt comprehensive utilization of resources rate, prolong mine work-ing life.
Embodiment:
Illustrate:
1, because underground rock salt component content is extremely inhomogeneous, add that the subsurface geology situation is complicated, the ore deposit alkali quantitative changeization of exploitation is big, and therefore the composition of embodiment ore deposit halogen is averaged herein.Herein among the embodiment, sodium sulfate type well mine salt composition is an example with the refreshing Salt Company of Huaian well mine, that is: the composition of ore deposit halogen be NaCl about 298g/l, Na
2SO
4Be 22g/l left and right sides CaSO
4For about 1.7g/l; Calcium sulfate type well mine salt composition is an example with the refreshing Salt Company of Huaian well mine, that is: the composition of ore deposit halogen be NaCl about 310g/l, Na
2SO
4For about 2.6g/l, CaSO
4For about 5.5g/l.Production factor is approximately 86%.
2, composition is inequality in the waste ammonia-soda solution of each ammonia alkali enterprise generation, and embodiment gets herein: soda ash output is got 600,000 t/, and waste ammonia-soda solution is measured 9m
3/ t soda ash, its composition is: CaCl
2105g/l, NaCl 50g/l; The ammonia alkali waste residue is measured 320kg/t soda ash (butt).
3, the quality of soda ash, solid salt, solid calcium and liquid salt is with reference to national standard in the example, and the liquid calcium quality is got CaCl
2270g/l, NaCl 110g/l; Get CaCl in the high calcium halogen
290g/l, NaCl 230g/l; Na in the low caldo
2SO
4 -Get about 6g/l, NaCl 310g/l.
4, technology is for what select in the example, and processing parameter and product production are the parameter of main material and product, are experimental datas.Therefore, during practical application, should be according to practical situation, technology, processing parameter and product production can suitably be adjusted.
Embodiment 1:
Illustrate: be the sodium sulfate type well mine salt, do not consider to produce liquid calcium and liquid salt product among this embodiment, also do not consider low other purposes of caldo.
Utilize solvay soda process to carry out bittern system alkali (Na
2CO
3), that is: be that raw material is produced soda ash with bittern (salt solution), Wingdale (generating unslaked lime and carbonic acid gas), ammonia through calcining.Ammonia is fed in the saturated aqueous common salt form ammoniated brine, feed carbonic acid gas again and generate solubleness less sodium bicarbonate precipitation and ammonium chloride solution; Again will be after filtration, the NaHCO that obtains of washing
3Small crystal, the reheat calcining makes the soda ash product, and the carbon dioxide that its process is emitted is recyclable to be recycled; To contain the filtrate and milk of lime [Ca (OH) 2] Hybrid Heating of ammonium chloride then, the ammonia of being emitted is recyclable to be recycled.Prepare alkali and other raw material is enough with the low caldo of 5L, obtain the solid sodium carbonate of about 1kg, simultaneously the waste residue (butt) of about 9L waste liquid of generation and 0.32kg.
The resulting merging waste liquid of 5 batches above alkali producing process (45L altogether) replaces fresh water to be injected into sodium sulfate type salt mine, and (fresh water is annotated the bittern composition of well exploitation: NaCl 298g/l, Na
2SO
4Adopt halogen 22g/l), production factor gets 0.86, obtains the high calcium brine (CaCl of 38.7L
290g/l, NaCl 230g/l), simultaneously in the underground salt chamber that stayed,
Wherein: the high calcium brine of 35.8L carries out vacuum evaporating crystalization, obtains 8.23kg sodium-chlor and 4.35kg Calcium dichloride dihydrate, in addition, and with the high calcium brine (CaCl of 2.9L
290g/l) with the high caldo (Na of 22.1L
2SO
422g/l) mix, form calcium sulfate precipitation and obtain the low caldo (Na of 25L according to 1: 7.6 volume ratio
2SO
46g/l), the production of returning ammonia alkali bittern legal system alkali is used.
The waste residue produced is injected the formed underground salt of above-mentioned steps chamber, or inject and common annotate well with fresh water and adopt formed salt chamber or depleted salt chamber after the halogen.
More than the condition of production of each process in the middle of 1 year as follows:
With the soda ash industrial scale is 600,000 t/, so: wherein need hang down about 3,000,000 m of caldo
3/ year is made raw material, will produce 5,400,000 m
3Solvay liquor and 19.2 ten thousand tons soda-manufacturing waste residue.5,400,000 m
3Solvay liquor replace fresh water to annotate well adopting halogen, consider that production factor gets 0.86, will obtain about 4,640,000 m
3High calcium halogen; 19.2 ten thousand tons the soda-manufacturing waste residue that produces injects the molten chamber of underground salt and stores up after pre-treatment.In addition, year needs 34.8 ten thousand m
3High calcium halogen and 265.2 ten thousand m
3High nitre halogen mixing denitration after, make 3,000,000 m
3Low caldo use for soda ash production; Remaining about 429.2 ten thousand m
3High calcium halogen be used for the coproduction of salt calcium, obtain the solid salt product of about 52.2 ten thousand tons solid Calcium dichloride dihydrate and 98.8 ten thousand tons.
Embodiment 2:
Illustrate: be the sodium sulfate type well mine salt, consider among this embodiment to produce liquid calcium, liquid salt product, and other purposes of low caldo.
Utilize solvay soda process to carry out bittern system alkali (Na
2CO
3), that is: be that raw material is produced soda ash with bittern (salt solution), Wingdale (generating unslaked lime and carbonic acid gas), ammonia through calcining.Ammonia is fed in the saturated aqueous common salt form ammoniated brine, feed carbonic acid gas again and generate solubleness less sodium bicarbonate precipitation and ammonium chloride solution; Again will be after filtration, the NaHCO that obtains of washing
3Small crystal, the reheat calcining makes the soda ash product, and the carbon dioxide that its process is emitted is recyclable to be recycled; To contain the filtrate and milk of lime [Ca (OH) 2] Hybrid Heating of ammonium chloride then, the ammonia of being emitted is recyclable to be recycled.Prepare alkali and other raw material is enough with the low caldo of 5L, obtain the solid sodium carbonate of about 1kg, simultaneously the waste residue (butt) of about 9L waste liquid of generation and 0.32kg.
The resulting merging waste liquid of 5 batches above alkali producing process (45L altogether) replaces fresh water to be injected into the sodium sulfate type salt mine (composition of well mine salt: NaCl 298g/l, Na
2SO
4Adopt halogen 22g/l), production factor gets 0.86, obtains the high calcium brine (CaCl of 38.7L
290g/l, NaCl 230g/l), simultaneously in the underground salt chamber that stayed,
Wherein: the high calcium brine of 32.9L carries out vacuum evaporating crystalization, obtains 7.27kg sodium-chlor and 3.03kg Calcium dichloride dihydrate and optional liquid calcium product 2.67L; 5.8L high calcium brine (CaCl
290g/l) with the high caldo (Na of 44.2L
2SO
422g/l) mix, form calcium sulfate precipitation and obtain the low caldo (Na of 50L according to 1: 7.6 volume ratio
2SO
46g/l), in these low caldos, have the low caldo of 25L to return the bittern of using as system alkali in the alkali producing process, the low caldo of 25L is used for common vacuum salt or ore deposit halogen day solar salt shan in addition.
The waste residue produced injected above-mentioned steps formed underground salt chamber or molten chamber or inject and common adopt formed salt chamber or molten chamber after the halogen with fresh water.
In addition, obtain optional liquid calcium product (CaCl more than
2270g/l) 2.67L, the liquid calcium product of 1.0L wherein and 15.67 high caldo (Na
2SO
422g/l) mix, form calcium sulfate precipitation and obtain 16.67L liquid salt (NaCl) product (the about 304g/l of NaCl) according to 1: 17.2 volume ratio.
More than the condition of production of each process in the middle of 1 year as follows:
The soda ash industrial scale is 600,000 t/, so: wherein need hang down about 3,000,000 m of caldo
3/ year is made raw material, will produce 5,400,000 m
3Solvay liquor and 19.2 ten thousand tons soda-manufacturing waste residue.5,400,000 m
3Solvay liquor replace fresh water to annotate well adopting halogen, consider that production factor gets 0.86, will obtain about 4,640,000 m
3High calcium halogen; 19.2 ten thousand tons the soda-manufacturing waste residue that produces injects the molten chamber of underground salt and stores up after pre-treatment.Here consider to have 3,000,000 m
3Other purposes of low caldo, so, year need 69.6 ten thousand m
3High calcium halogen and 530.4 ten thousand m
3High nitre halogen mixing denitration after, make 6,000,000 m
3Low caldo use for soda ash production and other chemical industry; Remaining about 394.4 ten thousand m
3High calcium halogen be used for the coproduction of salt calcium, obtain about 36.4 ten thousand tons solid Calcium dichloride dihydrate, 87.2 ten thousand tons solid salt product and 320,000 m
3Liquid calcium.310,000 m in the liquid calcium
3Liquid calcium in 200,000 m
3Liquid calcium for sale as product; And about 120,000 m
3Liquid calcium and 1,880,000 m
3High nitre halogen mixing denitration after, make 2,000,000 m
3The liquid salt product, for sale.
Embodiment 3:
Illustrate: be calcium sulfate type well mine salt, do not consider to produce liquid calcium among this embodiment
Utilize solvay soda process to carry out bittern system alkali (Na
2CO
3), that is: be that raw material is produced soda ash with bittern (salt solution), Wingdale (generating unslaked lime and carbonic acid gas), ammonia through calcining.Ammonia is fed in the saturated aqueous common salt form ammoniated brine, feed carbonic acid gas again and generate solubleness less sodium bicarbonate precipitation and ammonium chloride solution; Again will be after filtration, the NaHCO that obtains of washing
3Small crystal, the reheat calcining makes the soda ash product, and the carbon dioxide that its process is emitted is recyclable to be recycled; To contain the filtrate and milk of lime [Ca (OH) 2] Hybrid Heating of ammonium chloride then, the ammonia of being emitted is recyclable to be recycled.Prepare alkali and other raw material is enough with the bittern of 5L, obtain the solid sodium carbonate of about 1kg, simultaneously the waste residue (butt) of about 9L waste liquid of generation and 0.32kg.And the bittern of 5L is to inject sodium sulfate calcium salt mine (composition of well mine salt: NaCl310g/l, Na with fresh water
2SO
42.6g/l) under adopt halogen and obtain.
The resulting merging waste liquid of 5 batches above alkali producing process (45L altogether) replaces fresh water to be injected into the sodium sulfate calcium salt mine (composition of well mine salt: NaCl 310g/l, Na
2SO
42.6g/l) under adopt halogen, consider that production factor gets 0.86, obtain the high calcium brine (CaCl of 38.7L
2100g/l, NaCl 220g/l), simultaneously in the underground salt chamber that stayed,
Wherein: the high calcium brine of 38.7L carries out vacuum evaporating crystalization, obtains 8.51kg sodium-chlor and 5.23kg Calcium dichloride dihydrate.
The waste residue produced is injected the formed underground salt of above-mentioned steps chamber, or inject and common adopt formed salt chamber or depleted salt chamber after the halogen with fresh water.
More than the condition of production of each process in the middle of 1 year as follows:
The soda ash industrial scale is 600,000 t/, so: obtain about 3,000,000 m with adopting halogen under the fresh water injection sodium sulfate calcium salt mine
3/ year bittern (NaCl 310g/l, Na
2SO
42.6g/l) make the raw material of system alkali, will produce 5,400,000 m
3Solvay liquor and 19.2 ten thousand tons soda-manufacturing waste residue.5,400,000 m
3Solvay liquor replace fresh water to annotate well adopting halogen, consider production factor, will obtain 4,640,000 m
3High calcium halogen, the content of calcium chloride is about 100g/l in this high calcium halogen, sodium chloride content is used for the coproduction of salt calcium about 220g/l, obtain the solid salt product of about 62.8 ten thousand tons solid Calcium dichloride dihydrate and 102.1 ten thousand tons.And 19.2 ten thousand tons the soda-manufacturing waste residue that produces injects the molten chamber of underground salt and stores up after pre-treatment.
Embodiment 4:
Prerequisite: calcium sulfate type well mine salt, consider to produce the liquid calcium product in this example, then:
Utilize solvay soda process to carry out bittern system alkali (Na
2CO
3), that is: be that raw material is produced soda ash with bittern (salt solution), Wingdale (generating unslaked lime and carbonic acid gas), ammonia through calcining.Ammonia is fed in the saturated aqueous common salt form ammoniated brine, feed carbonic acid gas again and generate solubleness less sodium bicarbonate precipitation and ammonium chloride solution; Again will be after filtration, the NaHCO that obtains of washing
3Small crystal, the reheat calcining makes the soda ash product, and the carbon dioxide that its process is emitted is recyclable to be recycled; To contain the filtrate and milk of lime [Ca (OH) 2] Hybrid Heating of ammonium chloride then, the ammonia of being emitted is recyclable to be recycled.Prepare alkali and other raw material is enough with the low caldo of 5L, obtain the solid sodium carbonate of about 1kg, simultaneously the waste residue (butt) of about 9L waste liquid of generation and 0.32kg.And the bittern of 5L is to inject sodium sulfate calcium salt mine (composition of well mine salt: NaCl310g/l, Na with fresh water
2SO
42.6g/l) under adopt halogen and obtain.
The resulting merging waste liquid of 5 batches above alkali producing process (45L altogether) replaces fresh water to be injected into the sodium sulfate calcium salt mine (composition of well mine salt: NaCl 310g/l, Na
2SO
42.6g/l) under adopt halogen, consider that production factor gets the 0.86 high calcium brine (CaCl that obtains 38.7L
2100g/l, NaCl 220g/l), simultaneously in the underground salt chamber that stayed,
Wherein: the high calcium brine of 38.7L carries out vacuum evaporating crystalization, obtains 8.24kg sodium-chlor and 4.32kg Calcium dichloride dihydrate and optional liquid calcium (CaCl
2270g/l) product 2.5L.
The waste residue produced injected above-mentioned steps formed underground salt chamber or molten chamber or inject and common adopt formed salt chamber or molten chamber after the halogen with fresh water.
More than the condition of production of each process in the middle of 1 year as follows: the soda ash industrial scale is 600,000 t/, considers 300,000 m
3The liquid calcium product, so: inject with fresh water and to adopt halogen under the sodium sulfate calcium salt mine and obtain about 3,000,000 m
3/ year bittern (NaCl 310g/l, Na
2SO
42.6g/l) make the raw material of system alkali, will produce 5,400,000 m
3Solvay liquor and 19.2 ten thousand tons soda-manufacturing waste residue.5,400,000 m
3Solvay liquor replace fresh water to annotate well adopting halogen, consider production factor 0.86, will obtain 4,640,000 m
3High calcium halogen, the content of calcium chloride is about 100g/l in this high calcium halogen, sodium chloride content is used for the coproduction of salt calcium about 220g/l.Produce 300,000 m
3The liquid calcium product after, can also produce the solid salt product of about 50.8 ten thousand tons solid Calcium dichloride dihydrate and 98.9 ten thousand tons.And 19.2 ten thousand tons the soda-manufacturing waste residue that produces injects the molten chamber of underground salt and stores up after pre-treatment.
Claims (9)
1. utilize the combined cycle production technique of salt, alkali and the optional calcium product of sodium sulfate type well mine salt, it may further comprise the steps:
1), utilize solvay soda process to prepare alkali (Na with bittern
2CO
3), obtain solid sodium carbonate, produce waste ammonia-soda solution and ammonia alkali waste residue simultaneously,
2), the waste liquid of above step replaces fresh water to be injected into sodium sulfate type salt mine down-hole adopting halogen, obtain high calcium brine; Simultaneously stayed molten chamber underground, i.e. salt chamber,
3), above step 2) high calcium brine carry out vacuum-evaporation, cause crystallization, obtain solid sodium chloride and Calcium dichloride dihydrate and optional liquid calcium product, and/or
3 '), above step 2) high calcium brine and high caldo according to certain mixed, form calcium sulfate precipitation, remove the calcium sulfate precipitation thing, obtain low caldo and
4), waste residue that above step 1) is produced is infused in step 2) formed underground salt chamber, or inject other and annotate well with fresh water usually and adopt left salt chamber after the halogen.
2. according to the technology of claim 1, step 3 wherein ') low caldo return the bittern of using as system alkali in the step 1), perhaps be used for common vacuum salt or ore deposit halogen day solar salt shan.
3. according to the technology of claim 1, also be included in step 4) following steps 5 afterwards):
The liquid calcium product of above step 3) and high caldo form calcium sulfate precipitation and obtain liquid salt (NaCl) product according to certain mixed.
4. according to the technology of claim 1 or 3, wherein high caldo is adopted halogen and is obtained by fresh water being injected sodium sulfate type salt mine down-hole, simultaneously in the underground salt chamber that stayed.
5. according to any one described technology among the claim 1-4, wherein said salt chamber is the salt chamber that the salt mine has been stayed after the rational exploitation, or depleted salt chamber.
6. according to the technology of claim 1, wherein the bittern of step 1) is low caldo or saturated bittern or both combinations.
7. utilize the combined cycle production technique of salt, alkali and the optional calcium product of calcium sulfate type well mine salt, it may further comprise the steps:
1), utilize solvay soda process to prepare alkali (Na with bittern
2CO
3), obtain solid sodium carbonate, produce waste ammonia-soda solution and ammonia alkali waste residue simultaneously,
2), the waste liquid of above step replaces fresh water to be injected into calcium sulfate type salt mine down-hole adopting halogen, obtain high calcium brine, simultaneously in the underground salt chamber that stayed,
3), above step 2) high calcium brine carry out vacuum-evaporation, cause crystallization, obtain solid sodium chloride and Calcium dichloride dihydrate and optional liquid calcium product,
4), waste residue that above step 1) is produced is infused in step 2) formed underground salt chamber, or inject other and common annotate well with fresh water and adopt formed salt chamber after the halogen.
8. technology according to claim 7, wherein said salt chamber are the salt chambeies that the salt mine has been stayed after the rational exploitation, or discarded salt chamber.
9. according to the technology of claim 7, wherein the bittern of step 1) is to be injected into calcium sulfate type salt mine down-hole with fresh water to adopt halogen, the bittern that obtains.
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