CN108502902A - A kind of integrated conduct method of salt-making mother liquor and salt slurry - Google Patents
A kind of integrated conduct method of salt-making mother liquor and salt slurry Download PDFInfo
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- CN108502902A CN108502902A CN201810398046.1A CN201810398046A CN108502902A CN 108502902 A CN108502902 A CN 108502902A CN 201810398046 A CN201810398046 A CN 201810398046A CN 108502902 A CN108502902 A CN 108502902A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
- C01D3/16—Purification by precipitation or adsorption
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Abstract
The invention discloses a kind of salt-making mother liquor and the integrated conduct methods of salt slurry.The method of the present invention includes：It is the 20 ~ 40min of lime emulsifying of 30 ~ 100 mesh, purity more than 60% by the way that grain size is added into the emulsion tank for be loaded with salt-making mother liquor；Active ingredient calcium oxide and the mass ratio of magnesium ion in salt-making mother liquor are in lime（105~110）× purity：1；Substance after emulsification is pumped into mother liquor stirred tank, 3 ~ 5h is fully reacted under stirring, pH is adjusted to be removed completely to magnesium chloride more than 11.4；Slurry after reaction is pumped into former reaction container and mix with the pH former halogen for being 6.8 to be purified halogen after removing iron ion and manganese ion, the pH by supplementing lye control purification halogen is 9.6 ~ 10；Purification halogen is separated by solid-liquid separation, gained clear liquid is used for vacuum salt.The present invention is to salt-making mother liquor demagging significant effect, a series of at low cost, environmental protection pressures that the solid waste for being separated by solid-liquid separation thoroughly, not only eliminating gypsum press filteration system, while eliminating ground generation causes.
Description
Technical field
The invention belongs to salt making technology field more particularly to the integrated conduct methods of a kind of salt-making mother liquor and salt slurry.
Background technology
Yulin City is located at the most northern of Shaanxi Province, and the intersection in loess plateau and Mu us dese is national history
City known for cultural appeal, Yulin are national energy weight chemical bases, and a variety of subterranean resource aquatic weeds of coal, oil, natural gas, rock salt are hidden extremely rich
Richness is known as " Kuwait " of China.Yulin City rock salt is resourceful, has the characteristics that area is big, reserves are more, grade is high.It should
8854.55 hundred million tons of regional rock salt proved reserves, 6,000,000,000,000 tons of prospective reserves.Yulin salt mine object is mainly blocky halite, sylvite
And anhydrite, there are a small amount of carnallite and rinneite, the grade of ore largely to belong to primes, matter is pure, and sodium chloride content is up to
99.8%, minimum 81.46%, it is average 95% or more, it is world's salt mine fine work mineral deposit rarely seen in history.
Vacuum salt production is the major way of current rock salt salt manufacturing, using brine as raw material, it is heated, is evaporated, is crystallized,
Separation, drying are to obtain the process of sodium chloride.The mode of production of salt manufacturing is concentrated to chlorine using bittern evaporation as formant, by solution
Change sodium supersaturation and its crystallization is made to be precipitated, the indirect steam for evaporating generation enters next effect heating room shell side as heat source, evaporation
Process and so on to end effect.Each effect steam is from positive pressure successively to negative pressure（Vacuum）Passage, the indirect steam that end effect generates introduce
Mixing condenser, with discharge system after cooling water condensation, not condensing by vacuum pump set or steam jet pump extraction to ensure that it is born
Pressure（Vacuum）State ensures the effective temperature difference between each effect, realizes multiple-effect evaporation.
Raw material of the brine as salt manufacturing, quality produce salt manufacturing most important.For the rock salt in Yulin, brine is miscellaneous
Matter ingredient is neither saltcake type is also not exclusively gypsum mould, but calcium sulfate-calcium chloride-chloride-magnesium type, that is to say, that this type
Type salt mine brine belongs to calcium type brine, and calcium therein is existed with the pattern of calcium sulfate and calcium chloride.
Therefore, it needs to purify brine before carrying out salt manufacturing.Bittern purifying mode is net using underground at present
Change is handled, and using the molten chamber in underground as reactor, after adding sodium sulphate to be reacted with the calcium chloride of dissolution in noting well water, generates sulphur
Sour calcium realizes the purpose of deliming, calcium sulfate solubility characteristics is taken full advantage of, by solid formation Deposit of Calcium Sulfate in the molten bottom of chamber of salt well
Portion, the calcium sulfate in liquid phase return out ground.With the progress of vapo(u)rization system, calcium sulfate forms enrichment, Wo Mentong in evaporator
It crosses the mode arranged outside mother liquor and controls feed liquid gypsum content in evaporator, first through decanter centrifuge enrichment after mother liquor discharge, after centrifugation
Slurry enter plate and frame filter press, liquid phase enters former halogen bucket after alkali demagging and re-uses by adding, and has recycled fractional saturation brine.
Slurry after centrifugation is pressed dry through filter press is sent to the processing of industrial refuse field, and the magnesium, iron in rock salt are dissolved in brine and take halogen well out of.
Halogen impurities in water Ca after the purified treatment of underground2+1.5g/l、Mg2+0.4g/l、SO4 2-2.7g/l、Fe2+17mg/l。
In addition, in order to ensure finished product salt quality, ensure the long-period stable operation of production system, the brine after down-hole treatment
It is realized by way of sodium hydroxide is added in brine except iron, demanganization, the purpose for inhibiting magnesium ion enrichment.With evaporation process
Be carried out continuously, gypsum forms enrichment, the stable operation in order to ensure salt manufacturing vapo(u)rization system and salt quality in salt manufacturing feed liquid,
It is controlled by way of being arranged outside salt-making mother liquor.The outer discharge capacity of salt-making mother liquor about 70m3/ h, main component are calcium sulfate, chlorination
Calcium, magnesium chloride.The salt-making mother liquor of discharge isolates solid phase gypsum first by centrifugation, press filtration, and gypsum mud is deposited in plant area, then
Transport to industrial refuse factory focuses on.Calcium chloride in liquid phase is balanced by supplementing a certain amount of saltcake, and magnesium chloride is then
It is controlled by way of sodium hydroxide is added in centrifuge mother liquor, centrifugal clear liquid returns salt manufacturing vapo(u)rization system, press filtration clear liquid note
Well.
But for salt manufacturing manufacturing enterprise, the presence of magnesium ion can not only have an impact product quality, and magnesium from
Son is enriched in evaporating feed liquid can increase feed concentration, and the evaporation feed liquid elevation of boiling point, energy consumption is made to increase；It simultaneously can be in certain condition
Issuing unboiled water solution causes equipment to be corroded.This bittern purifying mode exposes problems in actual moving process：
（1）The gypsum that system generates is difficult to transport for the moment, is deposited in plant area, environmental protection pressure is huge, in addition since moisture content is larger
Be butt processing cost it is also more expensive；
（2）The enrichment of magnesium chloride causes the feed liquid elevation of boiling point, magnesium chloride that can hydrolyze, cause under certain temperature, pressure in system
Corrosion, injures evaporation equipment；
（3）Salt-making mother liquor centrifugation, filter-pressing device high failure rate, maintenance cost are big；
（4）It is costly with sodium hydroxide demagging in mother liquor, and precipitate it is slower, in centrifugal clear liquid containing a large amount of gypsum and
Magnesium hydroxide solid formation returns to salt making system and forms vicious circle.
" greenization cleans " is the target that salt industry is pursued, and as environmental requirement is increasingly strict, is taken to carry out cycle
Control measure based on economy, energy-saving and emission-reduction reduce resource consumption, reduce environmental pollution, reinforcement environmental protection, realization economy,
The coordination sustainable development of society and environment, has been the inevitable choice of new century industry.Salt technique is being produced by raw material of rock salt
The calcium and magnesium mud and gypsum mud of by-product in production process are solved in the process, it has also become all salt making enterprises faces including Yulin Prefecture
The great environmental issue faced.
Invention content
The purpose of the present invention is to provide a kind of salt-making mother liquor and the integrated conduct methods of salt slurry, it is intended to solve above-mentioned background
Existing deficiencies in the technology in technology.
The invention is realized in this way the integrated conduct method of a kind of salt-making mother liquor and salt slurry, this method includes following step
Suddenly：
（1）Into the emulsion tank for be loaded with salt-making mother liquor be added grain size be 30 ~ 100 mesh, purity more than 60% lime emulsifying 20 ~
40min；Wherein, magnesium ion concentration is 0.38 ~ 0.42g/L in the salt-making mother liquor, in the lime active ingredient calcium oxide with
The mass ratio of magnesium ion is in salt-making mother liquor（105~110）× purity：1；
（2）Substance after emulsification is pumped into mother liquor stirred tank, 3 ~ 5h is fully reacted under stirring, pH is adjusted to be more than 11.4
It is removed completely to magnesium chloride；
（3）Slurry after reaction is pumped into former reaction container after being mixed with the pH former halogen for being 6.8 to remove iron ion and manganese ion
It is purified halogen, the pH by supplementing lye control purification halogen is 9.6 ~ 10；Purification halogen is subjected to solid-liquid in Dorr thickener
Separation, gained clear liquid are used for vacuum salt.
In the present invention, the salt-making mother liquor includes calcium sulfate, calcium chloride, magnesium chloride iron ion and manganese ion ingredient.
Preferably, in step（3）Further include step later：（4）In the case of halogen-extracting pump normal water filling, by step（3）
The sediment obtained after middle separation of solid and liquid is pumped sediment to the outlet of halogen-extracting pump by high pressure injection pulp pump, and the sediment is together with water filling
Into halogen underground.
In the present invention, the sediment obtained after separation of solid and liquid is salt slurry, and main component includes calcium and magnesium mud and gypsum mud, is passed through
The mode that salt slurry is noted to well solves the problems, such as that waste solids are overstock.
Preferably, in step（1）In, magnesium ion concentration is 0.4g/L in the salt-making mother liquor, in the lime effectively at
It is 107 × purity to divide the mass ratio of calcium oxide and magnesium ion in salt-making mother liquor：1.
Preferably, in step（1）In, the outer discharge capacity of the salt-making mother liquor is 68 ~ 72m3/h。
For deficiency of the prior art, the present invention, according to defect analysis, will eliminate defect during research and development
It should set about from the following aspect：
（1）The outer discharge capacity of salt-making mother liquor is continuous, stablizes, and evaporator gypsum content will be stablized；
（2）Again it finds demagging agent and replaces liquid caustic soda, it is ensured that magnesium hydroxide can precipitate, limpid into tank brine, while to reduce and remove
Magnesium expense；
（3）The whereabouts for thoroughly solving gypsum is eliminated and generates a series of environmental issues that gypsum solid waste causes in production process；
（4）Feed liquid content of magnesium chloride in evaporator is effectively controlled by demagging, eliminating hydrolysis of magnesium chloride can cause equipment to corrode
Hidden danger；
（5）The mode that well is noted by using calcium and magnesium mud bans mother liquor centrifugation, press filteration system, eliminates operating cost and the repair of great number
Expense, it is synchronous to eliminate a series of vicious circles caused by separation of solid and liquid is not thorough.
In addition, the present invention is directed to former halogen composition characteristic, in view of following reason, CaSO4、CaCl2、MgCl2Not in former halogen
Reason, and handled in the mother liquor being discharged after salt manufacturing evaporation and concentration：
Reason one：According to former halogen composition characteristic, CaSO is removed in former halogen4、CaCl2、MgCl2, processing cost is too high, uneconomical；
Reason two：Impurity content in former halogen is in undersaturated condition, will not cause the fouling of halogen transportation pipeline；
Reason three：Salt manufacturing vapo(u)rization system uses gypsum seed antiscaling process, CaSO in former halogen4、CaCl2、MgCl2It is evaporated in salt manufacturing
It carries out forming enrichment with evaporation in tank, and has solid phase CaSO4It is precipitated, then by the lithoexpulsium paste system of evaporator with gypsum material
Liquid form is discharged, solid phase CaSO in the gypsum feed liquid of discharge4A concentration of 20 ~ 30g/l, CaCl in liquid phase2、MgCl2Content exist
10g/l or less；This discharge gypsum liquid sinks the solid salt of salt device separation through 11 meters of layers of salt manufacturing, then by pipeline to press filteration system,
Centrifugal clear liquid is by dereaction bucket after the demagging of liquid feeding alkali, a small amount of saltcake deliming of supplement, in feelings of the control purification halogen pH 9.5 ~ 9.7
Under condition, the purpose realized except iron, demanganization is synchronized；Slurry after centrifugation enters press filtration, realizes and is separated by solid-liquid separation, and liquid phase removes note well water
Bucket, solid phase go to gypsum stockyard.
Compared with the prior art the shortcomings that and deficiency, the invention has the advantages that：
（1）The present invention passes through a large amount of laboratory test, and demagging, demagging effect are successfully finally realized in salt-making mother liquor with lime
Significantly, it 100% removes, and cost is relatively low, is separated by solid-liquid separation thorough；Realizing a large amount of recycling mother liquors（Old halogen）, heat recovery profit
With while demagging, significantly reduce demagging cost, purification halogen turbidity is substantially reduced, mother liquor demagging significant effect, is steamed to be follow-up
The stable operation of hair system and product quality provide guarantee, meet the requirement of national energy conservation and emission reduction and environmental protection, benefit higher, city
Field foreground is more preferable；
（2）The present invention not only eliminates gypsum press filteration system, while the system that the solid waste for eliminating ground generation causes
Row environmental protection pressure.
（3）Present invention process is simple, with obvious effects, stable and reliable operation, is a kind of ideal solution gypsum solid waste
The technology of whereabouts.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
1 experimental verification of embodiment
1, operation principle and experiment before preparation
（1）MgCl2, Fe, Mn processing method
Using lime（Main component CaO）Method removes MgCl2, chemical equation is：
CaO + H2O=Ca（OH)2 Digest exothermic reaction
MgCl2 + Ca（OH)2 =Mg（OH)2↓ + CaCl2（It is newborn）
It being learnt by literature search, to achieve the purpose that demagging, the pH of solution is necessary >=and 11.3.Practical original halogen usage amount in production
For 530m3The salt-making mother liquor amount of/h or so, generation are 70m3/ h or so, salt-making mother liquor amount are 13% or so of former halogen amount.Before experiment
MgCl in the former halogen of detection2Content is 1.6g/l or so, into salt manufacturing evaporator after to evaporate rich product content and increase be about MgCl in former halogen2
Ten times of content.
（2）Micro Fe, the processing method of Mn
When former 9.2 >=pH of halogen >=8.7 range, so that it may remove major part Fe, Mn, salt quality is entirely capable of meeting user's requirement.
Implementing method：Using adding the mother liquor after lime demagging（PH is 11.3 or so）The method mixed with former halogen can realize that removing Fe removes Mn,
When mixed purification halogen pH is not achieved 8.7, by supplementing liquid caustic soda on a small quantity（Sodium hydroxide）Mode adjusted.
（3）CaCl2Processing method
Using saltcake（Na2SO4）Method removes CaCl2, chemical equation is：
CaCl2+Na2SO4= 2NaCl+CaSO4↓
This method has nearly 5 years time in the application of the Yulin Zhong Yan company, simple for process, reliable, while can balance lime introducing
Calcium ion.
（4）The heavy salt device of salt manufacturing takes mother liquor composition：
Ca2+：3.058g/l Mg2+：2.238g/l SO4 2-：3.089g/l
CaCl2：4.899 g/l MgCl2：8.767 g/l CaSO4：4.378 g/l
NaCl：299.76 g/l pH：8.2
2, experimental procedure
（1）Sample preparation：
The sample preparation 1. lime is milled, it is spare；
2. taking gypsum mother liquor fraction, filter, clear liquid is spare；
3. take analysis pure cerium hydroxide sodium, be configured to 30% liquid caustic soda it is spare；
4. taking analytically pure sodium sulphate spare in right amount；
5. the gypsum mother liquor in the heavy salt device of the amount of taking fully salt manufacturing is spare.
（2）Lime removes the magnesium ion in gypsum mother liquor with sodium hydroxide except the magnesium ion Comparability test in gypsum mother liquor, stone
Ash removes the magnesium ion in mother liquid filtrate with sodium hydroxide except the magnesium ion Comparability test in mother liquid filtrate：
1. calculating the amount of lime that theoretical demagging needs, when the digestion of lime 100% is calcium hydroxide solution, remove in 1 liter of mother liquor
The calcium oxide of 5.22g need to be added in the magnesium ion of 2.238 g/l, but calcium hydroxide is also micro-soluble material, and conversion can not be achieved 100%,
Therefore it to realize demagging purpose, can only be solved by the method for controlling pH, according to demagging experience, i.e. by 11.3 or more pH modulation
It can；
2. taking four beakers, number 1#, 2#, 3#, 4#, 1#, 2# measure 1 liter of gypsum mother liquor and 1 liter of mother liquor filtering with graduated cylinder respectively
Clear liquid；3#, 4# also measure 1 liter of gypsum mother liquor respectively and 1 liter of mother liquor crosses cleaner liquid；
3. being slowly added to the calcium oxide weighed in 1# beakers, pH meter is observed while stirring, control reaction speed is intended to
The larger magnesium hydroxide of crystal grain is obtained, calcium oxide 27.08g is consumed altogether until pH is adjusted to 11.4（It does not digest, in solid form
Addition）；
4. being crossed in 2# and being slowly added to lime in cleaner liquid（Digestion）, pH meter is observed while stirring, until pH is adjusted to 11.4,
Consumption calcium oxide 21.07g altogether；
5. 30% sodium hydroxide solution is added in 3#, 4# gypsum mother liquor and excessively cleaner liquid respectively, pH to 11.4 is adjusted to compare；
6. it is respectively that the slurry agitation after being reacted in above-mentioned 1# ~ 4# beakers is uniform, pour into observation sedimentation, separation in 1 liter of graduated cylinder
Effect；
7. timing simultaneously records clarification liquid level, it is as shown in table 1 below that clarification liquid level changes over time trend：
Table 1
8. separately taking 1 liter of gypsum mother liquor, it is slowly added to the postdigestive lime that is milled under the premise of continuously stirring, adjusts pH to 11.4,
Then the calcium chloride amount that demagging new life is calculated according to stoichiometric relationship adds calcium chloride amount in original nut liquid（10.35+4.899=
15.249）, the two needs sodium sulphate 19.5g altogether, weighs 19.5g and analyzes pure saltcake, is added after dissolving, observation sedimentation, separating effect,
As shown in table 2 below：
Table 2
| Time | 5min | 10min | 15min | 20min | 1h |
| Clarify liquid level | 21% | 38% | 50% | 59% | 76% |
9. simulating sediment note well experiment, the sediment after taking 1# to settle takes appropriate note well water that 1 liter of liquid level scale, observation sedimentation is added
Effect, clear liquid liquid level 84% after 1h, significant effect, the rate of settling are as shown in table 3 below：
Table 3
| Time | 5min | 10min | 15min | 20min | 1h |
| Clarify liquid level | 36% | 60% | 71% | 76% | 84% |
10. taking 1.5 liters of gypsum mother liquor, postdigestive lime is added while stirring, pH to 11.4 is adjusted, is then added dissolved
Sodium sulphate 29.3g delimings, the gypsum mother liquor after reaction are spare；The gypsum mother liquor 130ml after Mixed bittern 870ml and reaction is taken respectively
（70m by volume3:500 m3It calculates）It pours into and stirs 1min in beaker, be subsequently poured into timing in 1 liter of graduated cylinder, observation precipitation point
From effect, while the gypsum liquid after 1 liter of demagging, deliming being taken to be compared, sedimentation separation rate is as shown in table 4 below：
Table 4
| Time | 5min | 10min | 15min | 20min | 1h |
| Liquid level is clarified after being mixed with former halogen | 95% | 96% | 96% | 97% | 97.1% |
| Gypsum mother liquor clarifies liquid level | 20% | 32% | 40% | 49% | 72% |
Gypsum mother liquor is very fast with the mixed rate of settling of former halogen after lime demagging saltcake deliming, rear clear liquid body in 5min
Product is up to, up to 97.1%, the compactness of precipitation is good, and supernatant is limpid, has obtained good effect after 95%, 1h.
3, data analysis
（1）Clear liquid analyzes data after 1# sedimentations（g/l）, as shown in table 5 below：
Table 5
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 6.07 | It is not detected | 0.576 | 16.14 | It is not detected | 0.816 | 300.86 | 11.76 |
（2）Clear liquid analyzes data after lime demagging, saltcake deliming sedimentation（g/l）, as shown in table 6 below：
Table 6
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 1.966 | It is not detected | 3.141 | 1.82 | It is not detected | 4.45 | 285.35 | 12 |
（3）Sedimentation clear liquid analysis data after note well water is mixed with sediment（g/l）, as shown in table 7 below：
Table 7
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 3.32 | It is not detected | 2.66 | 6.12 | It is not detected | 3.77 | 66.81 | 12.4 |
（4）Sedimentation separation clear liquid analyzes data after gypsum mother liquor after demagging deliming is mixed with manifold halogen（g/l）, such as the following table 8 institute
Show：
Table 8
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 2.01 | 0.212 | 3.47 | 1.56 | 0.83 | 4.92 | 301.04 | 9.3 |
4, conclusion (of pressure testing)
（1）The magnesium ion in gypsum mother liquor can be removed completely by selecting lime to be demagging agent；
（2）Lime demagging effect of settling is much more with obvious effects than sodium hydroxide demagging, and sedimentation separation is thorough, and obtained clear liquid exists
80%（Volume ratio）More than, be conducive to the recycling of mother liquor；
（3）When using lime demagging, the calcium carbonate of reaction is not participated in, calcium hydroxide has and helps heavy effect well；
（4）After lime and saltcake demagging, deliming, obtained clear liquid quality is preferable, and data are shown in Table 5, and magnesium ion removes completely,
Calcium ion is down to 1.966g/l compared with mother liquor by former 3.058g/l, and pH=12 can recycle completely；
（5）It uses the gypsum mother liquor after sodium sulphate deliming to be mixed with former halogen again using the lime elder generation demagging digested, is more advantageous to hydrogen
The sedimentation of magnesia and ferrous sulfide, sedimentation separation effect is very good, and the compactness of precipitation is good, and solid concentration is only 3%, is better than
Existing purification halogen effect of settling, obtained brine is limpid, pH 10.3, can be realized under the premise of complete demagging except iron, be removed
The purpose of manganese；
（6）After lime and saltcake demagging, deliming, obtained calcium and magnesium gypsum mud note well is feasible；
（7）Process of the lime except demagging in gypsum mother liquor is verified, digestion reaction and demagging reaction concentration are made whether feasible；
Scene takes salt-making mother liquor several, and chemical examination ingredient is as shown in table 9 below：
Table 9
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 3.52 | 3.14 | 2.51 | 6.85 | 12.30 | 3.56 | 299.47 | 8.1 |
By calculating, it is directly added into according to excessive 50% lime, 70% lime 17g, saltcake 27g is weighed, then directly by stone
Ash is added in gypsum mother liquor, continuously stirs, and pH=9 after 1h, growing way is very slow, and next day measures pH=11.8.To prove：It is indigested
The direct demagging of lime takes a long time, and reaction rate is very slow.Therefore, lime slaking program is carried out first during demagging.
（8）It uses brine and mother liquor to digest lime respectively, sees demagging effect, take 1 liter of gypsum mother liquor（Content of magnesium chloride in mother liquor
8.767g/l）, weigh 70% lime 17g（It is added according to excessive 50%）, first with 1:3 are digested, and mother liquor is then added, stirring
After 30min, then 27g saltcake is added in pH=11.4, after settling 1h, for clear liquid amount 70% or more, analysis data see the table below 10 institutes
Show：
Table 10
| Ca2+ | Mg2+ | SO4 2- | CaCl2 | MgCl2 | CaSO4 | NaCl | pH |
| 1.83 | It is not detected | 2.72 | 1.93 | 0 | 3.85 | 302.66 | 12.2 |
Conclusion：Ineffective mother liquor or former halogen, can all digest lime, the reaction time is suitable.
（9）It separately verifies with 1:2、1:Volume change situation after 3 former halogen digestion lime, takes two parts of lime 20g, adds respectively
Enter 40ml and 60ml original halogen to be digested, postdigestive volume increases by 8% and 12.5%, therefore the volume of digester should be in theoretical base
Increase on plinth.
（10）Verify influence of the content of magnesium chloride raising to the rate of settling
Mother liquor was newly taken with heavy salt device March 26（Magnesium chloride 12.3g/l）With former halogen according to 1:1 liter of mother liquor is added after 3 digestion lime
In（Magnesium chloride 12.3g/l）, pH obtains 11.7 after the former stirs 24min, and pH obtains 11.4 after the latter stirs 45min, adds respectively
Enter 27g saltcake stirring 5min, pours into 1 liter of graduated cylinder and observe effect of settling, as shown in table 11 below：
Table 11
| Time | 5min | 10min | 15min | 20min | 1h |
| Liquid level is clarified after being mixed with former halogen | 0.8cm | 1.4cm | 2.0cm | 2.5cm | 6.5cm |
| Gypsum mother liquor clarifies liquid level | 1.2cm | 2.5cm | 3.5cm | 4.0cm | 11.0cm |
According to above-mentioned data it is found that after content of magnesium chloride is increased to 12.3g/l in mother liquor, the lime slaking by excessive 50% adds
Enter that rear clarifying effect is bad, and the rate of settling is slow, therefore, has to consider to work as content of magnesium chloride during using lime demagging
Reaction, effect of settling after raising.
In order to further verify influence of the precipitation capacity to clarifying effect of generation, above-mentioned reaction Mother liquor 700ml is taken, is added
300ml original halogen is diluted, significant effect, as shown in table 12 below：
Table 12
| Time | 5min | 10min | 15min | 20min | 1h |
| Clarify liquid level | 2.5cm | 4.3cm | 6.5cm | 8.3cm | 25cm |
Then 700ml mother liquors are taken（Magnesium chloride 12.3g/l）, add former halogen 300ml, content of magnesium chloride be adjusted to 8.91g/l, is added
Lime after excessive 50% digestion is added saltcake and stirs 5min, sees clarifying effect, same notable after 1 hour.
Experiments have shown that：Density of magnesium chloride is low, is conducive to effect of settling.
（11）Lime particle degree is increased（It is changed to 0.6mm or more）, it is added according to excessive 100%, pH increases very slow
（It not readily dissolves）, when content of magnesium chloride is higher, effect of settling is without significant change（5-10min effect of settling）.
（12）On March 21st, 2016, by being calcined to existing analytically pure calcium oxide, verification sucrose method measures to be had in lime
The feasibility of calcium oxide is imitated, by calcining in 1 hour, the content of the efficient oxidation calcium was 90% or so, it was confirmed that survey using sucrose method
It is feasible to determine the efficient oxidation calcium in lime.
（13）Prepare the calcium oxide sample of 30 mesh, 60 mesh and 100 mesh respectively by the method for screening, it is laggard through digesting respectively
Row demagging, consumption amount of lime are suitable, it was demonstrated that when granularity is in 30 ~ 100 mesh, are influenced less on reaction, therefore, production process can
Select the lime of 30 ~ 100 mesh as demagging agent.
2 industrialization of embodiment is run
1, lime demagging operating condition
According to laboratory simulation experiment conclusion, demagging agent selects grain size in 30 ~ 100 mesh, and purity is more than 70% lime；It first will system
Salt mother liquor is pumped into mother liquor by mother liquor relay pump and is stirred to react bucket, content of magnesium chloride in mother liquor is obtained by analysis, according to chemistry
Excessive 50% lime is added in quantitative relation, and lime first emulsifies 30 minutes through emulsion tank, is then pumped by emulsification pump
Mother liquor is stirred to react bucket, and opening stirring makes fully to react.4 as a child detections are stirred to react magnesium ion in barrel slurry and are not detected, pH
More than 11.4, it is then turned on processing Mother liquor delivery pump and is sent to former reaction container.
2, brine recycling and turbidity situation of change
Treated, and mother liquor enters reaction container except iron, demanganization, and pH value has not yet been reached 9.2 or more, can only pass through the side of supplement liquid caustic soda
Formula improves purification halogen pH, and by one month trial operation, liquid caustic soda was averaged addition in 0.9m3/h（25% liquid caustic soda）, dongle sedimentation
The slagging amount of device（Sediment）Do not increase not only, reduce again instead, average slagging amount is 14m3/ h, disposing mother liquor utilization rate exist
80% or more.Solid phase gypsum（Sediment）Enter underground together in company with note well water, falls to the molten bottom of chamber portion of salt well, eliminate ground stone
The generation of cream solid waste solves a series of environmental issues of gypsum solid waste initiation.
After the present invention puts into operation 24 hours, purification halogen turbidity is decreased obviously, as clear as crystal, has obtained expected mesh completely
's.The outer lithoexpulsium paste mother liquor of salt making system is continuous, stablizes, is controllable, and demagging removes iron, deliming process stable operation, stone of thoroughly having stopped transport
Cream press filteration system.
This invention removes salt-making mother liquor centrifugation, press filtration processes, simplify mother liquor treatment process, have saved operating cost；
The present invention changes mother liquor demagging agent, keeps certain amount coarseness heavy insoluble matter in demagging process, it is heavy to play the role of helping, and adds
The speed sedimentation of magnesium hydroxide, significantly reduces demagging cost；Treated, and mother liquor is directly entered former halogen settler, and salt slurry plays
Heavy effect is helped, the rate of settling is accelerated, improves sediment compactness, salt-making mother liquor recycling is realized, it is turbid to reduce brine
Degree.
3, Economic and Efficiency Analysis
（1）Cost of raw and processed materials compares
Materials procurement expense of the present invention is determined by the norm quota of consumption and prediction markets price, returns to mother liquor amount per hour in 70m3/ h is left
The right side, for saltcake to the price at factory according to 240 yuan/ton, lime to 570 yuan/ton of the price at factory, liquid caustic soda folding hundred arrives 3700 yuan/ton of the price at factory, production system
Effective production time based on 330 days/year.
Saltcake usage amount increases 8m in original basis3/ h, mean concentration is with 249kg/m3Meter, 1.992 tons of saltcake prices
478.08 yuan, increase by 478.08 yuan of expenses per hour；Lime consumption is（4 tons/class）0.5 ton/when, increase by 285 yuan per hour；It is former
0.52 ton of liquid caustic soda consumption/when（Folding hundred）, at present 0.25 ton of dosage/when（Folding hundred）, 0.27 ton of reduction/when（Folding hundred）, drop per hour
Low 999 yuan；After the present invention is implemented, because eliminating the serial equipments such as horizontal spiral centrifuge, plate and frame filter press, year maintenance cost can
It reduces by 700,000, replaces filter cloth expense every year about 15.6 ten thousand, it is accumulative to save 85.6 ten thousand yuan/year of maintenance of equipment expense.Raw material expense
Total cost is reduced per hour with average（999-478.08-285）=235.92 yuan/hour, the accumulative expense 186.85 that saves material
Ten thousand yuan/year.
（2）Artificial and welfare fund with it is original substantially quite.
（3）The gypsum treatment expense of reduction
Gypsum mother liquor 70m is discharged in salt manufacturing per hour3/ h, the brine rate of recovery are new to generate amount of gypsum 14m in terms of 80%3/ h, original centrifugation,
Gypsum total amount after press filtration handles gypsum expense per ton in terms of 50 yuan, at least to spend processing cost every year at least at 20,000 tons/year
1000000 yuan, and eliminate every environmental protection punishment due to storing, transporting initiation and bad social influence.
（4）The electricity charge are calculated
Through practical measurement, former power consumption sets substantially suitable with existing current consuming apparatus power consumption.
Present invention process is simple, easy to operate, considers above-mentioned expense, can save 372.45 ten thousand yuan in year.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (4)
1. the integrated conduct method of a kind of salt-making mother liquor and salt slurry, which is characterized in that this approach includes the following steps：
（1）Into the emulsion tank for be loaded with salt-making mother liquor be added grain size be 30 ~ 100 mesh, purity more than 60% lime emulsifying 20 ~
40min；Wherein, magnesium ion concentration is 0.38 ~ 0.42g/L in the salt-making mother liquor, in the lime active ingredient calcium oxide with
The mass ratio of magnesium ion is in salt-making mother liquor（105~110）× purity：1；
（2）Substance after emulsification is pumped into mother liquor stirred tank, 3 ~ 5h is fully reacted under stirring, pH is adjusted to be more than 11.4
It is removed completely to magnesium chloride；
（3）Slurry after reaction is pumped into former reaction container after being mixed with the pH former halogen for being 6.8 to remove iron ion and manganese ion
It is purified halogen, the pH by supplementing lye control purification halogen is 9.6 ~ 10；Purification halogen is subjected to solid-liquid in Dorr thickener
Separation, gained clear liquid are used for vacuum salt.
2. the integrated conduct method of salt-making mother liquor as described in claim 1 and salt slurry, which is characterized in that in step（3）Later
It further include step：
（4）In the case of halogen-extracting pump normal water filling, by step（3）The sediment obtained after middle separation of solid and liquid passes through high pressure injection pulp pump
Sediment is pumped to the outlet of halogen-extracting pump, the sediment enters halogen underground together with water filling.
3. the integrated conduct method of salt-making mother liquor as described in claim 1 and salt slurry, feature are only, in step（1）In,
Magnesium ion concentration is 0.4g/L in the salt-making mother liquor, active ingredient calcium oxide and magnesium ion in salt-making mother liquor in the lime
Mass ratio is 107 × purity：1.
4. the integrated conduct method of salt-making mother liquor as claimed in claim 3 and salt slurry, which is characterized in that in step（1）In, institute
It is 68 ~ 72m to state the outer discharge capacity of salt-making mother liquor3/h。
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| CN110963521A (en) * | 2019-12-30 | 2020-04-07 | 自贡市轻工业设计研究院有限责任公司 | Extraction process of calcium chloride in yellow brine salt-making mother liquor |
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| CN110963521B (en) * | 2019-12-30 | 2022-06-14 | 自贡市轻工业设计研究院有限责任公司 | Extraction process of calcium chloride in yellow brine salt-making mother liquor |
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