CN108862393A - A method of manganese carbonate is prepared using Mn-bearing waste water - Google Patents
A method of manganese carbonate is prepared using Mn-bearing waste water Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01G45/00—Compounds of manganese
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
- C02F1/64—Heavy metal compounds of iron or manganese
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/722—Oxidation by peroxides
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- C02F2301/00—General aspects of water treatment
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Abstract
The present invention relates to a kind of methods for preparing manganese carbonate using Mn-bearing waste water.This approach includes the following steps：Anionic surfactant is added into waste water and ammonium hydrogen carbonate is reacted, is separated by solid-liquid separation, obtains carbonic acid manganese filter cake.The method provided by the invention for preparing manganese carbonate using Mn-bearing waste water, it is mainly reacted using manganese and the ammonium hydrogen carbonate condition existing for anionic surfactant in waste water to optimize the Precipitation process of manganese carbonate, product analysis shows, gained manganese carbonate category trigonal system, calcite crystal form, appearance is rounded, appearance consistency and dispersing uniformity are obviously improved compared with conventional precipitation method, improve the grade and the added value of industry of manganese carbonate product.
Description
Technical field
The invention belongs to wastewater utilization fields, and in particular to a method of manganese carbonate is prepared using Mn-bearing waste water.
Background technique
Manganese metal is a kind of important industrial chemicals, wide in all kinds of chemical field applications such as steel, non-ferrous metal, food
It is general.Global manganese resource is abundant, and about 5.7 hundred million tons of manganese ore reserves, but distributional region otherness is larger, and South Africa manganese resource occupies the world
First of, next is followed successively by the countries such as Ukraine, Australia, Brazil, India, China, Gabon, Mexico, while high-grade manganese
Resource focuses primarily upon the countries such as South Africa and Ukraine to mine (manganese content > 40%), and the manganese resource in China is predominantly low-grade
Manganese ore (manganese content < 30%), China's lean ore account for about nearly the 93.6% of national manganese ore gross reserves.
It makes steel industry and be unable to do without manganese, China's steel industry develops rapidly nearly ten years, and iron and steel output hits new peak repeatly.2010
China's crude steel yield is more than 6.2 hundred million tons, and crude steel yield in 2014 reaches 8.23 hundred million tons, 2017 annual 8.317 hundred million tons of yield of crude steel.
With the continuous expansion of steel production capacity, China's manganese ore import volume, which also synchronizes, to climb up and up, and China's manganese ore import volume in 2007 is only
It is 6,640,000 tons, is up to 2125.86 ten thousand tons to the import volume of manganese ore year in 2017, import volume increases by 220% during the decade.
Currently, in the operation process of industries such as electrolytic manganese, sulfuric acid legal system titanium dioxide, anisaldehyde production, Process of Hydroquinone Production
A large amount of Mn-bearing waste water can be generated, the direct emission of these Mn-bearing waste waters not only would seriously pollute the environment, but also waste preciousness
Promoter manganese.Using Mn-bearing waste water as raw material, realize that the recycling of manganese contemplates that more considerable environmental benefit and economic benefit.
In various manganese products, the industrial application of manganese carbonate is relatively broad, may be used as base manure, seed soaking, seed dressing, top dressing with
And the sprinkling on blade face, the growth of crop can be promoted and increase yield；In animal husbandry and feed industry, it is used as feed addictive；
Simultaneously manganese carbonate be also process paint, ink drier, the raw material of bitter edible plant acid manganese solution, electrolytic manganese raw materials for production and manufacture it
The raw material of his manganese salt；In addition, manganese carbonate can also be used in papermaking, ceramics, printing and dyeing, ore floatation, battery, smelt catalyst, analysis
Reagent, mordant, additive, pharmaceutic adjuvant etc..
Publication No. is that the patent application of CN105967396A discloses a kind of processing method of Mn-bearing waste water, is to electrolysis
In the Mn-bearing waste water that manganese process generates, ammonium hydroxide is added and contains CO2Production exhaust gas handled, obtain manganese carbonate solid and demanganization
Solution.This method be prepare manganese carbonate using liquid-phase precipitation method, though available manganese carbonate product, gained manganese carbonate product
Adhesion effect is obvious, and appearance, the crystal form consistency of product are poor, and product added value is low, leads to the economic effect of respective handling method
Benefit is not significant, and the practical ranges of manganese carbonate product are also restrained.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for preparing manganese carbonate using Mn-bearing waste water, to solve existing liquid phase
The precipitation method to Mn-bearing waste water handled existing for product dispersion effect difference problem, existing method can also be solved and prepare carbonic acid
The problem of appearance consistency existing for manganese, crystal form consistency difference.
To achieve the above object, the technical scheme adopted by the invention is that：
A method of manganese carbonate being prepared using Mn-bearing waste water, is included the following steps：Anionic surface is added into waste water
Activating agent and ammonium hydrogen carbonate are reacted, and are separated by solid-liquid separation, are obtained carbonic acid manganese filter cake.
The method provided by the invention for preparing manganese carbonate using Mn-bearing waste water mainly utilizes the manganese and bicarbonate in waste water
Ammonium condition existing for anionic surfactant is reacted to optimize the Precipitation process of manganese carbonate, product analysis table
Bright, gained manganese carbonate category trigonal system, calcite crystal form, appearance is rounded, and appearance consistency and dispersing uniformity are more conventional
Intermediate processing is obviously improved, and improves the grade and the added value of industry of manganese carbonate product.
The temperature of the reaction is 20-60 DEG C, and reaction time 0.3-1h is aged 1-3h after reaction.It, can in reaction process
Control system pH is 6.0-8.0, with the better progress for promoting reaction.It is furthermore preferred that control system pH is 7.2.
For the Precipitation process for advanced optimizing manganese, the rate of recovery of manganese ion is improved, reduces other impurities ion concentration,
Preferably, the temperature of the reaction is 30-35 DEG C, and the temperature of the ageing is 40-50 DEG C.It is furthermore preferred that the temperature of the reaction
Degree is 33.3 DEG C, and the time of reaction is 0.5h；The temperature of the ageing is 45 DEG C, and the time of ageing is 2h.
In general, ammonium hydrogen carbonate is added in the form of ammonium bicarbonate soln, the dosage of ammonium hydrogen carbonate is relative to thick manganese sulfate
Mn in mother liquor2+Should be excessive, to promote Mn2+Abundant recycling.Preferably, ammonium hydrogen carbonate and Mn2+The ratio between mole be
(0.5-2):1, preferably 1.1:1.
From the aspect of cost and the preparation effect of manganese carbonate, it is preferred that the anionic surfactant is anion
Polyacrylamide, sodium laurate, neopelex, NaLS, lauryl sodium sulfate, fatty alcohol polyoxy second
At least one of alkene ether sulfuric ester salt, alkyl alcohol ethoxylates phosphate ester salt.It is furthermore preferred that the anion surface active
Agent is lauryl sodium sulfate and/or neopelex.The mole of the anionic surfactant is Mn2+Mole
0.01-0.1 times of amount.
For the Precipitation time for further decreasing manganese carbonate, reaction efficiency is improved, convenient for the progress of subsequent reactions, preferably
, Mn in the waste water2+Content be at least 0.5mol/L, it is furthermore preferred that at least 1.0mol/L.Such as Mn2+Content meet
Above-mentioned condition, directly progress subsequent reactions.Such as Mn2+Content be lower than above-mentioned content, then waste water can be carried out at concentration
Reason, to realize above-mentioned purpose.
Carbonic acid manganese filter cake is successively washed, alcohol is washed and is dried to get manganese carbonate finished product.
Currently, many industries, such as the production of electrolytic manganese, sulfuric acid legal system titanium dioxide, anisaldehyde, Process of Hydroquinone Production industry,
The processing problem of Mn-bearing waste water is all referred to, Mn-bearing waste water, which removes, contains Mn2+Except, it is also possible to contain Al3+、Fe3+、Mg2+Equal metals from
Sub- impurity, for a certain specific Mn-bearing waste water, after determining species of metal ion, can first remove metal in Mn-bearing waste water from
Sub- impurity, then the step of above-mentioned addition anionic surfactant and ammonium hydrogen carbonate are reacted is carried out, it can both mention in this way
The purity of high carbon acid manganese product, also may be implemented the comprehensive reutilization of metallic element in different type waste water.
The present invention lists the process situation of the waste water containing following common metal ion impurity, for other metal ions,
It can refer to the prior art or following process situation handle connatural metal ion.
(1) contain Ca in the Mn-bearing waste water2+And/or Mg2+, it is anti-that precipitating reagent progress removing calcium and magnesium is added into Mn-bearing waste water
It answers.
It is energy and Ca that removing calcium and magnesium, which reacts related precipitating reagent,2+、Mg2+Form the not soluble in water or extremely difficult reaction for being dissolved in water
Reagent.It can be to contain oxalate denominationby (C2O4 2-), oxalic acid hydrogen radical (HC2O4 -), fluorine ion (F-) acid, soluble metal
Double salt etc. that salt, soluble ammonium salt, soluble metal double salt, metal ion and ammonium ion are formed, it is preferred that the precipitating reagent is
Oxalic acid (H2C2O4), potassium oxalate (K2C2O4), potassium binoxalate (KHC2O4), sodium oxalate (Na2C2O4), sodium bioxalate (NaHC2O4), grass
Sour ammonium ((NH4)2C2O4), ammonium binoxalate (NH4HC2O4), potassium ferric oxalate (K3Fe(C2O4)3), iron ammonium oxalate ((NH4)3Fe
(C2O4)3), hydrofluoric acid, potassium fluoride, sodium fluoride, at least one of ammonium fluoride.From the effect aspect of deliming magnesium ion, more
Preferably, the precipitating reagent is at least one of ammonium oxalate, ammonium binoxalate, ammonium fluoride.
By taking ammonium fluoride as an example, main chemical reactions involved in the step are：
Ca2++2F-→CaF2↓ Ksp=3.45*10-11
Mg2++2F-→MgF2↓ Ksp=5.16*10-11
In the step, Ca in the dosage view system of precipitating reagent2+、Mg2+Content determine, be usually slightly larger than theoretical amount i.e.
Can, it such as may be selected to be 1.05 times of precipitating reagent theoretical amount.After removing calcium and magnesium reaction, made a return journey by the means such as filtering, being centrifugated
Subsequent processing is carried out except sediment, then to the waste water after removing calcium and magnesium.
(2) contain heavy metal ion in the Mn-bearing waste water, ammonium sulfide is added to Mn-bearing waste water and carries out removing heavy metals reaction.
The heavy metal ion includes Cr3+、Cu2+、Ni2+At least one of.
Removing heavy metals react related main chemical reactions：
2Cr3++3S2-→Cr2S3↓
Cr2S3+6H2O→2Cr(OH)3+3H2S↑
Cu2++S2-→ CuS ↓ Ksp=1.9*10-33
Ni2++S2-→ NiS ↓ Ksp=2.79*10-39
In general, ammonium sulfide is added in waste water to be processed in the form of ammonium sulfide solution.The additional amount of ammonium sulfide can press
Theoretical dosage is pressed according to stoichiometric ratio or slightly more than theoretical dosage is added.The temperature of the removing heavy metals reaction is 50-70 DEG C, instead
It is 1-3h between seasonable.The pH of removing heavy metals reaction controlling system is neutrality.In the step, the reaction of control removing heavy metals is above-mentioned anti-
It is carried out under the conditions of answering, heavy metal ion (such as Cr in waste water that step 1) processing can be made to obtain3+, Cu2+、Ni2+Deng) formed and sunk
It forms sediment, while avoiding Mn2+Manganese sulfide precipitating is formed, to realize the removal of the heavy metal ion impurities such as copper, nickel.Still more preferably
, the temperature of the removing heavy metals reaction is 60 DEG C, reaction time 2h.
After removing heavy metals reaction, sediment is removed by the means such as filtering, being centrifugated, then to useless after removing heavy metals
Water carries out subsequent processing.
(3) contain Fe in the Mn-bearing waste water3+And/or Al3+, ammonium hydroxide is added into Mn-bearing waste water and carries out except iron reactive aluminum.
Be added ammonium hydroxide to system pH be 5-6.The temperature except iron reactive aluminum is 85-95 DEG C, time 0.5-2h.With
It is reacted under upper reaction condition, the Fe in waste water solution can be made3+、Al3+It is converted into hydroxide precipitating while avoiding Mn2+Form hydrogen
Manganese oxide precipitating.Preferably, except the temperature of iron reactive aluminum is 90 DEG C, time 1h.
Except the main chemical reactions that iron reactive aluminum is related to are as follows：
Fe3++3OH-→Fe(OH)3↓ Ksp=2.79*10-39
Al3++3OH-→Al(OH)3↓ Ksp=1.9*10-33
Ksp indicates solubility product constant in formula.
In such a case, as Mn-bearing waste water also contains Fe2+, before ammonium hydroxide is added, oxidant is first added by Fe2+Oxygen
Turn to Fe3+.Main chemical reactions involved in the process are as follows：
2Fe2++H2O2+2H+→2Fe3++2H2O
The selection of oxidant is not particularly limited, from cost, the convenient aspect of operation, it is preferred that the oxidant is
Hydrogen peroxide.The hydrogen peroxide that mass content is 28-30% generally can be used.The additional amount of hydrogen peroxide can be according to the color change of waste water
It determines, when waste water becomes bronzing from bottle green completely, i.e., provable Fe2+Oxidation is complete.
After iron reactive aluminum, sediment is removed by being separated by solid-liquid separation, then carry out subsequent processing to except the waste water after iron aluminium.
It is generated for the waste water for containing above-mentioned impurity metal ion simultaneously, such as sulfuric acid legal system titanium dioxide process useless containing manganese
Water, can successively carry out above-mentioned oxidation processes, except iron reactive aluminum, removing heavy metals reaction, removing calcium and magnesium reaction come realize step by step separation remove
The classification of miscellaneous and various metallic elements recycles.For Ca in waste water2+、Mg2+Content is few or Fe3+、Al3+It is poor
Situation optionally proceeds as described above, to simplify the treatment process of waste water, reduces technological operation step.
The Mn-bearing waste water generated for sulfuric acid legal system titanium dioxide process, it is preferred that except iron reactive aluminum uses ammonium hydroxide, except a huge sum of money
Belong to reaction and use ammonium sulfide, removing calcium and magnesium reaction uses ammonium class precipitating reagent, prepares manganese carbonate reaction using ammonium hydrogen carbonate, in this way can be with
Utmostly reduce the introduction volume of foreign ion.To prepare manganese carbonate reaction after obtain filtrate (separation carbonic acid manganese filter cake after institute
) be evaporated, ammonium sulfate can be recycled.
Recycling ammonium sulfate concrete operation step be：Filtrate is evaporated under reduced pressure through Rotary Evaporators to most of solute and is precipitated
When, hot suction filtration is carried out to system, filter cake is washed, dries and can obtain ammonium sulfate.Carbonic acid manganese filter cake is washed with deionized extremely
Barium chloride solution is added in washing lotion and muddiness does not occur.The mass fraction of the barium chloride solution is 5-10%.With anhydrous after washing
Ethanol washing filter cake 3-4 times, then in 60 DEG C of vacuum drying 8h to get product manganese carbonate.Five oxidations two may be selected in drying process
The conventional dryings agent such as phosphorus.
Specifically, the Mn-bearing waste water generated for sulfuric acid legal system titanium dioxide process, can realize iron using method of the invention
The classification recycling of aluminium, calcium and magnesium, ammonium sulfate improves to obtain the by-products such as iron oxide red, cement gypsum industry raw material, nitrogenous fertilizer raw material
The added value and wastewater treatment economic benefit of recovery product have good popularization and application foreground.
The process flow of other kinds of Mn-bearing waste water can refer to the useless containing manganese of above-mentioned sulfuric acid legal system titanium dioxide process generation
The roadmap of water utmostly improves the utilization of metallic element in waste water, is realizing from the thinking of comprehensive reutilization
While wastewater treatment, the economy of processing is taken into account, and then realizes the scientific of Mn-bearing waste water, synthesization, valueization processing.
Detailed description of the invention
Fig. 1 is the process flow chart of the method that manganese carbonate is prepared using Mn-bearing waste water of embodiment 1；
Fig. 2 is manganese carbonate product and the XRD spectrum of standard PDF card 44-1472；
Fig. 3 is the TGA map of manganese carbonate product；
Fig. 4 is to add surfactant products therefrom (a) and do not add the SEM comparison diagram of surfactant products therefrom (b)；
Fig. 5 is that the SEM of 23 products therefrom of embodiment schemes.
Specific embodiment
Embodiments of the present invention are described further with reference to the accompanying drawing.In following embodiment, with sulfuric acid legal system titanium
For the Mn-bearing waste water that white powder process generates, the preparation process of manganese carbonate is illustrated.
Mn-bearing waste water comes from Luohe Xingmao Titanium Industry Co., Ltd.'s sulfuric acid legal system titanium dioxide process, mainly contains Mn2+、Fe2 +、Fe3+、Al3+, also contain calcium and magnesium ion, other heavy metal ion impurities such as Yi Jitong, chromium, nickel, Mn2+Concentration is 13.2gL-1, iron ion, aluminium composition are respectively 5.01gL-1, 3.4gL-1。
The mass fraction of ammonium hydroxide is 25-28%；Ammonium sulfide solution presses body by the dense ammonium sulfide solution and water of commercially available 20wt%
Product is than being 1:2 mix；The mass fraction of ammonium bicarbonate soln is 10%.
Embodiment 1
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, process flow chart is as shown in Figure 1, using following step
Suddenly：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium fluoride solution that 10ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After mixing 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, obtain dense
Contracting liquid；
4) 0.045 times of Mn is added into concentrate2+The lauryl sodium sulfate of molar concentration and the ammonium hydrogen carbonate of 77ml are molten
Liquid adjusts pH value of solution to 7.0,45 DEG C of ageing 2h, ageing knot is warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.58g, the manganese ion rate of recovery are 97.25%, product after beam
Manganese ion content is 43.52% in manganese carbonate.
Fe (OH) is precipitated as obtained by step 1)3、Al(OH)3, can further recycle iron oxide red.Insoluble calcium and magnesium obtained by step 3)
Precipitating can be applied to cement gypsum industry.The filtrate obtained after step 4) ageing filtering, obtains by-product sulphur after evaporative crystallization
Sour ammonium is used as nitrogenous fertilizer raw material.
Embodiment 2
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) is same as Example 1；
Step 4)：0.045 times of Mn is added into concentrate2+The lauryl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 6.0, is warming up to 45 DEG C of ageing 2h, ageing knot at being 30 DEG C in reaction temperature after stirring 0.5h
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.4885g, the manganese ion rate of recovery are 90.99%, production after beam
Manganese ion content is 42.23% in object manganese carbonate.
Embodiment 3
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) is same as Example 1；
Step 4)：0.045 times of Mn is added into concentrate2+The lauryl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 6.5, is warming up to 45 DEG C of ageing 2h, ageing knot at being 30 DEG C in reaction temperature after stirring 0.5h
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.5532g, the manganese ion rate of recovery are 94.08%, production after beam
Manganese ion content is 42.56% in object manganese carbonate.
Embodiment 4
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) is same as Example 1；
Step 4)：0.045 times of Mn is added into concentrate2+The lauryl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 7.5, is warming up to 45 DEG C of ageing 2h, ageing knot at being 30 DEG C in reaction temperature after stirring 0.5h
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.6441g, the manganese ion rate of recovery are 97.32%, production after beam
Manganese ion content is 42.51% in object manganese carbonate.
Embodiment 5
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) is same as Example 1；
Step 4)：0.045 times of Mn is added into concentrate2+The lauryl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 8.0, is warming up to 45 DEG C of ageing 2h, ageing knot at being 30 DEG C in reaction temperature after stirring 0.5h
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.6557g, the manganese ion rate of recovery are 97.61%, production after beam
Manganese ion content is 42.45% in object manganese carbonate.
Embodiment 6
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium fluoride solution that 10ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After mixing 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, obtain dense
Contracting liquid；
4) 0.045 times of Mn is added into concentrate2+The neopelex of molar concentration and the ammonium hydrogen carbonate of 77ml
Solution adjusts pH value of solution to 7.0, is warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 30 DEG C in reaction temperature, is aged
After filter, filter cake is washed, alcohol is washed, is dried, it is final that product 2.565g, the manganese ion rate of recovery are 96.74%, produce
Manganese ion content is 43.57% in object manganese carbonate.
Embodiment 7
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 6 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The neopelex of molar concentration and the carbonic acid of 77ml
Hydrogen ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 20 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.5487g, the manganese ion rate of recovery are
94.84%, manganese ion content is 42.98% in product manganese carbonate.
Embodiment 8
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 6 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The neopelex of molar concentration and the carbonic acid of 77ml
Hydrogen ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 40 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.50g, the manganese ion rate of recovery are
92.43%, manganese ion content is 42.71% in product manganese carbonate.
Embodiment 9
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 6 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The neopelex of molar concentration and the carbonic acid of 77ml
Hydrogen ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 50 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.494g, the manganese ion rate of recovery are
91.42%, manganese ion content is 42.34% in product manganese carbonate.
Embodiment 10
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 6 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The neopelex of molar concentration and the carbonic acid of 77ml
Hydrogen ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 60 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.499g, the manganese ion rate of recovery are
90.51%, manganese ion content is 41.83% in product manganese carbonate.
Embodiment 11
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium fluoride solution that 10ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After mixing 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, obtain dense
Contracting liquid；
4) 0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the ammonium hydrogen carbonate of 77ml are molten
Liquid adjusts pH value of solution to 7.0,45 DEG C of ageing 2h, ageing knot is warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.578g, the manganese ion rate of recovery are 97.235%, production after beam
Manganese ion content is 43.57% in object manganese carbonate.
Embodiment 12
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 11 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 1h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.276g, the manganese ion rate of recovery are 85.78%,
Manganese ion content is 43.53% in product manganese carbonate.
Embodiment 13
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 11 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 1.5h after being stirred to react 0.5h at being 30 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.4987g, the manganese ion rate of recovery are
94.35%, manganese ion content is 43.61% in product manganese carbonate.
Embodiment 14
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 11 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution, adjusting pH value of solution to 7.0 are warming up to 45 DEG C of ageing 2.5h after being stirred to react 0.5h at being 30 DEG C in reaction temperature,
It filters, filter cake is washed, alcohol is washed, is dried after ageing, it is final that product 2.6341g, the manganese ion rate of recovery are
97.45%, manganese ion content is 42.73% in product manganese carbonate.
Embodiment 15
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 11 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 77ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 3h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.6975g, the manganese ion rate of recovery are
97.46%, manganese ion content is 41.73% in product manganese carbonate.
Embodiment 16
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium fluoride solution that 10ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After mixing 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, obtain dense
Contracting liquid；
4) 0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the ammonium hydrogen carbonate of 77ml are molten
Liquid adjusts pH value of solution to 7.0,45 DEG C of ageing 2h, ageing knot is warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature
It filters, filter cake is washed, alcohol is washed, is dried, final that product 2.5872g, the manganese ion rate of recovery are 97.26%, production after beam
Manganese ion content is 43.42% in object manganese carbonate.
Embodiment 17
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 16 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 63ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 2h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.4367g, the manganese ion rate of recovery are
86.18%, manganese ion content is 40.85% in product manganese carbonate.
Embodiment 18
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 16 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 70ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 2h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.5578g, the manganese ion rate of recovery are
92.86%, manganese ion content is 41.93% in product manganese carbonate.
Embodiment 19
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 16 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 84ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 2h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.6105g, the manganese ion rate of recovery are
97.21%, manganese ion content is 43.01% in product manganese carbonate.
Embodiment 20
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
Step 1)-step 3) and embodiment 16 are consistent.
Step 4)：0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the bicarbonate of 91ml
Ammonium salt solution adjusts pH value of solution to 7.0, and 45 DEG C of ageing 2h are warming up to after being stirred to react 0.5h at being 30 DEG C in reaction temperature, old
It filters, filter cake is washed, alcohol is washed, is dried after change, it is final that product 2.6632g, the manganese ion rate of recovery are
98.21%, manganese ion content is 42.59% in product manganese carbonate.
Embodiment 21
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium fluoride solution that 10ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After mixing 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, obtain dense
Contracting liquid；
4) 0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the ammonium hydrogen carbonate of 77ml are molten
Liquid adjusts pH value of solution to 7.2, is warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 33.3 DEG C in reaction temperature, is aged
After filter, filter cake is washed, alcohol is washed, is dried, it is final that product 2.6244g, the manganese ion rate of recovery are 98.91%,
Manganese ion content is 43.53% in product manganese carbonate.
Embodiment 22
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, using following steps：
1) iron aluminium is removed：150ml Mn-bearing waste water is placed in a beaker, be added 30wt% hydrogenperoxide steam generator 15.5ml until
Waste water becomes bronzing from bottle green；Adjust pH between 5-6 with ammonium hydroxide, after system react to after 1h standing at 90 DEG C to room
Temperature filters after removing insoluble matter, obtains filtrate A；
2) removing heavy metals：3ml ammonium sulfide solution is added into the filtrate A that step 1) obtains and is filtered after 60 DEG C of reaction 2h
Insoluble heavy metal precipitation object is removed, liquor B is obtained；
3) removing calcium and magnesium：The ammonium oxalate solution that 5ml concentration is 0.1mol/L is added into liquor B, is stirred at 3000r/min
After 15min, it is filtered to remove insoluble impurities, obtains liquor C, liquor C is concentrated into Mn2+Concentration be 1mol/L, be concentrated
Liquid；
4) 0.045 times of Mn is added into concentrate2+The dodecyl sodium sulfate of molar concentration and the ammonium hydrogen carbonate of 77ml are molten
Liquid adjusts pH value of solution to 7.2, is warming up to 45 DEG C of ageing 2h after being stirred to react 0.5h at being 33.3 DEG C in reaction temperature, is aged
After filter, filter cake is washed, alcohol is washed, is dried, it is final that product 2.5374g, the manganese ion rate of recovery are 93.72%,
Manganese ion content is 42.66% in product manganese carbonate.
Embodiment 23
The method for preparing manganese carbonate using Mn-bearing waste water of the present embodiment, substantially the same manner as Example 21, difference is only that,
In step 4), the surfactant used is analysis virgin pp amide, is purchased from the limited public affairs of Shanghai Aladdin biochemical technology share
Department, additional amount Mn2+0.08 times of molar concentration.It is final that product 2.5823g, the manganese ion rate of recovery are 95.02%, product carbon
Manganese ion content is 43.48% in sour manganese.
Comparative example
The method for preparing manganese carbonate using Mn-bearing waste water of this comparative example, using following steps：
Step 1)-step 3) and embodiment 21 are consistent.
Step 4)：The ammonium bicarbonate soln of 77ml is added into concentrate, adjusts pH value of solution to 7.2, is in reaction temperature
Be stirred to react at 33.3 DEG C after 0.5h and be warming up to 45 DEG C of ageing 2h, filtered after ageing, filter cake is washed, alcohol is washed,
Dry, final that product 2.5947g, the manganese ion rate of recovery are 96.64%, manganese ion content is 43.02% in product manganese carbonate.
Test example 1
This test example analyzes the property of 21 gained manganese carbonate product of embodiment using inductive coupling plasma emission spectrograph
Energy index, the results are shown in Table 1.
The ICP-AES analysis of manganese carbonate obtained by 1 embodiment of table
As shown in Table 1, in manganese carbonate product obtained by embodiment, total impurity ion content≤0.6% meets work
Industry manganese carbonate (HG/T 4203-2011) quality standard.
Test example 2
This test example carries out XRD analysis to the product of embodiment 21 and TGA is analyzed, as a result as shown in Figures 2 and 3.
As shown in Figure 2, the characteristic peak one of the diffraction maximum of product manganese carbonate XRD spectrum and manganese carbonate standard PDF card 44-1472
One is corresponding, and diffraction peak intensity is big, free from admixture peak, illustrates the purity is high of sediment and is the high manganese carbonate of crystallinity, belongs to three prismatic crystals
System, calcite crystal form.
From the figure 3, it may be seen that manganese carbonate is decomposed since 200 DEG C, it is warm with being decomposed obtained by Literature Consult to 500 DEG C close to constant weight
Degree is consistent.
Test example 3
This test example carries out sem analysis to manganese carbonate product obtained by embodiment 21 and comparative example, as a result as shown in figure 4, its
Middle Fig. 4 (a) is embodiment 21, and Fig. 4 (b) is comparative example.The SEM figure of 23 gained manganese carbonate product of embodiment is as shown in Figure 5.
As can be seen that the manganese carbonate that the surfactants such as addition lauryl sodium sulfate obtain is rounded, dispersion effect
Preferably；And the product adhesion effect that is not added with surfactant is obvious and spherical, rectangular distributes alternately；Add surfactant institute
Product crystal form is substantially better than and is not added with surfactant products obtained therefrom.
In the other embodiments of the method for preparing manganese carbonate using Mn-bearing waste water of the invention, grass is can be used in removing calcium and magnesium reaction
Sour hydrogen ammonium is replaced the ammonium oxalate in embodiment 22, can also can be with Ca with other2+、Mg2+Reaction forms insoluble matter
Reagent is replaced, such as oxalic acid, potassium oxalate, potassium binoxalate, sodium oxalate, sodium bioxalate, potassium ferric oxalate, iron ammonium oxalate.It is added
Other anionic surfactants may be selected in the step of ammonium hydrogen carbonate is reacted, such as anionic polyacrylamide, sodium laurate
It can disperse the actual conditions such as consistency according to product Deng, specific dosage be adjusted, can be obtained and the comparable effect of embodiment.It removes
The conditions such as reaction temperature, time involved in iron aluminium process and removing heavy metals process, the condition that can be limited according to the present invention into
Row is adaptively adjusted, and can obtain and the comparable treatment effect of embodiment.
Above implementations show the treatment process of the Mn-bearing waste water generated for sulfuric acid legal system titanium dioxide process, Qi Tahan
Manganese waste water, such as the Mn-bearing waste water that the production of electrolytic manganese, anisaldehyde, Process of Hydroquinone Production industry generate can refer to the reality of examples detailed above
Apply mode, orderly remove other metal ions, while realizing metal ion classified use, realize high-purity, high-crystallinity,
The preparation of the manganese carbonate product of high consistency.
Claims (10)
1. a method of manganese carbonate is prepared using Mn-bearing waste water, which is characterized in that is included the following steps：Yin is added into waste water
Ionic surface active agent and ammonium hydrogen carbonate are reacted, and are separated by solid-liquid separation, are obtained carbonic acid manganese filter cake.
2. the method for preparing manganese carbonate using Mn-bearing waste water as described in claim 1, which is characterized in that the temperature of the reaction
It is 20-60 DEG C, reaction time 0.3-1h is aged 1-3h after reaction.
3. the method for preparing manganese carbonate using Mn-bearing waste water as claimed in claim 2, which is characterized in that the temperature of the reaction
It is 30-35 DEG C, the temperature of the ageing is 40-50 DEG C.
4. the method for preparing manganese carbonate using Mn-bearing waste water as described in claim 1, which is characterized in that the reaction is in pH
It is carried out under conditions of 6.0-8.0.
5. the method for preparing manganese carbonate using Mn-bearing waste water as described in claim 1, which is characterized in that the anionic surface
Activating agent is anionic polyacrylamide, sodium laurate, neopelex, NaLS, dodecyl sulphate
At least one of sodium, polyoxyethylene alkyl ether sulfate salt, alkyl alcohol ethoxylates phosphate ester salt.
6. the method as claimed in claim 1 or 5 for preparing manganese carbonate using Mn-bearing waste water, which is characterized in that the anion
The mole of surfactant is Mn2+0.01-0.1 times of mole.
7. the method according to any one of claims 1 to 5 for preparing manganese carbonate using Mn-bearing waste water, which is characterized in that described
Contain Ca in Mn-bearing waste water2+And/or Mg2+, precipitating reagent is added into Mn-bearing waste water and carries out removing calcium and magnesium reaction.
8. the method according to any one of claims 1 to 5 for preparing manganese carbonate using Mn-bearing waste water, which is characterized in that described
Contain heavy metal ion in Mn-bearing waste water, ammonium sulfide is added to Mn-bearing waste water and carries out removing heavy metals reaction.
9. the method according to any one of claims 1 to 5 for preparing manganese carbonate using Mn-bearing waste water, which is characterized in that described
Contain Fe in Mn-bearing waste water3+And/or Al3+, ammonium hydroxide is added into Mn-bearing waste water and carries out except iron reactive aluminum.
10. the method for preparing manganese carbonate using Mn-bearing waste water as claimed in claim 9, which is characterized in that Mn-bearing waste water also contains
There is Fe2+, before ammonium hydroxide is added, oxidant is first added by Fe2+It is oxidized to Fe3+。
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| CN112174180A (en) * | 2020-09-06 | 2021-01-05 | 桂林理工大学 | Preparation method and application of calcite-rhodochrosite solid solution |
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| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109279656A (en) * | 2018-10-25 | 2019-01-29 | 中国科学院青海盐湖研究所 | The mesoporous ball-type Mn of micro-nano2O3Preparation method |
| CN112174180A (en) * | 2020-09-06 | 2021-01-05 | 桂林理工大学 | Preparation method and application of calcite-rhodochrosite solid solution |
| CN113735138A (en) * | 2021-09-18 | 2021-12-03 | 青海中迪跃科技有限公司 | Method for treating ammonia distillation wastewater |
| CN113735138B (en) * | 2021-09-18 | 2023-08-22 | 青海中迪跃科技有限公司 | Ammonia distillation wastewater treatment method |
| CN114715943A (en) * | 2022-03-28 | 2022-07-08 | 中南大学 | Process for selectively recovering manganese from manganese-containing wastewater and preparing manganese chloride and preparation method |
| CN115108570A (en) * | 2022-06-17 | 2022-09-27 | 中南大学 | Process for preparing basic magnesium carbonate and ammonium sulfate by innocent treatment in manganese-containing wastewater |
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