CN106006694A - Technology for producing calcium carbonate from calcinator gas and calcium sulfate - Google Patents
Technology for producing calcium carbonate from calcinator gas and calcium sulfate Download PDFInfo
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- CN106006694A CN106006694A CN201610352968.XA CN201610352968A CN106006694A CN 106006694 A CN106006694 A CN 106006694A CN 201610352968 A CN201610352968 A CN 201610352968A CN 106006694 A CN106006694 A CN 106006694A
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- calcium carbonate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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Abstract
The invention discloses a technology for producing calcium carbonate from calcinator gas and calcium sulfate. The technology comprises the following steps: enabling the calcinator gas and brine to react for 2-8 hours at 25-60 DEG C, wherein sodium hydroxide in the brine reacts with the calcinator gas to obtain reaction liquid, the reaction liquid contains sodium sulfate, sodium chloride, sodium nitrate, sodium carbonate and calcium sulfate, and the sodium carbonate and calcium sulfate in the reaction liquid react for 2-8 hours at 25-60 DEG C to generate a suspension containing calcium carbonate precipitate; performing solid-liquid separation of the suspension to obtain calcium carbonate precipitate and mother liquid respectively; washing the calcium carbonate precipitate with fresh water at 20-90 DEG C; performing solid-liquid separation to obtain washed calcium carbonate and washing liquid; and drying the washed calcium carbonate at 120-160 DEG C to obtain a product of calcium carbonate, and mixing the washing liquid with the production wastewater to dissolve raw ore containing sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide and calcium sulfate. The technology disclosed by the invention has the advantages of reasonable technology, low production cost, high added value, cyclic economy of waste utilization and environmental friendliness.
Description
Technical field
The invention belongs to technical field of inorganic chemical industry, particularly a kind of calciner gas produces calcium carbonate with calcium sulfate
Technique.
Background technology
Known with sodium chloride-sodium sulfate-water (NaCl-Na2SO4-H2O) system (containing a small amount of magnesium sulfate,
Calcium sulfate impurity) bittern purifying technique remove calcium sulfate impurity method have: with NaCl-Na2SO4-H2O system (contains
Have a small amount of magnesium sulfate, calcium sulfate impurity) and soda (Na2CO3) reaction removing calcium sulfate impurity；With
NaCl-Na2SO4-H2O system (containing a small amount of magnesium sulfate, calcium sulfate impurity) and Calx (Ca (OH)2)、
Natrii Sulfas (Na2SO4), carbon dioxide (CO2) reaction removing magnesium sulfate, calcium sulfate impurity, abbreviation Calx-
Natrii Sulfas-flue gas method.Wherein, Method of Soda exist chemical agent costly, production cost high problem；Calx-awns
Nitre-flue gas method exists that energy consumption cost is high, calcium and magnesium body refuse can not utilize and become waste residue and need process problem.Cause
This, above-mentioned technique cost in production application is high, calcium and magnesium body refuse needs to process.
Summary of the invention
It is an object of the invention to provide a kind of calciner gas and produce calcium carbonate technique with calcium sulfate, it has raw material
Cheap strong adaptability, furnace gas and the comprehensive utilization of calcium body refuse, rational technology, production cost are low, added value of product
The feature such as height, twice laid recycling economy, environmental friendliness.
For achieving the above object, the present invention takes techniques below scheme:
A kind of calciner gas produces calcium carbonate technique with calcium sulfate, and it comprises the following steps:
A. soda calcining furnace produce calciner gas with containing sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide,
The salt of calcium sulfate, reacts 2-8 hour at 25-60 DEG C, and the sodium hydroxide in salt is anti-with calciner gas
Reactant liquor should be obtained, containing sodium sulfate, sodium chloride, sodium nitrate, sodium carbonate, calcium sulfate in this reactant liquor；
B. the sodium carbonate in this reactant liquor and calcium sulfate react 2-8 hour at 25-60 DEG C, and reaction generation contains
The suspension of precipitation of calcium carbonate；
C. this suspension of solid-liquid separation, respectively obtains lime deposit and mother solution；
D. being washed with fresh water by this lime deposit, wash temperature is 20-90 DEG C, and solid-liquid separation obtains
Wash rear calcium carbonate and cleaning mixture；
E. this is washed rear calcium carbonate and be dried to obtain product calcium carbonate through 120-160 DEG C；
F. this cleaning mixture with produce waste water mix with dissolving sulfur acid sodium, sodium chloride, sodium nitrate, sodium hydroxide,
The raw ore of calcium sulfate.
CO in described calciner gas2Concentration is 70-80%.
In described salt, the content of each component is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、NaCl
5-320g/l、NaOH 0.2-10.0g/l、Ca2SO4 0.3-7.0g/l。
In described reactant liquor, each composition weight content is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、
NaCl 5-320g/l、Na2CO3 0.27-13.25g/l、Ca2SO4 0.3-7.0g/l。
In described mother solution, each composition weight content is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、
NaCl 5-320g/l。
Described production waste water is the mother solution in described step C.
Present invention process can also be other loads containing carbon dioxide for the alternative as calciner gas
Body；Present invention process can also be Na for the alternative as above-mentioned salt2SO4、NaNO3、NaCl、NaOH、
Ca2SO4In containing Na2SO4、NaNO3, NaOH, Ca of NaCl one of which salt2SO4Carrier.
The invention has the beneficial effects as follows: in present invention process flow process, the calciner gas that soda calcining furnace produces (contains
There is high concentration CO2Deng composition) with salt (containing sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, sulphuric acid
The compositions such as calcium) it is raw material production calcium carbonate product, there is cheaper starting materials strong adaptability, furnace gas and calcium body refuse and combine
Closing and utilize, rational technology, production cost are low, added value of product is high, twice laid recycling economy, environment friend
The feature such as good.
Detailed description of the invention
Hereinafter only for several embodiments, the present invention is described in detail, but it is not intended to limiting the invention
Practical range.
Embodiment 1: take 1600m3Calciner gas (CO2Concentration 75%) and 1000m3Salt is (containing Na2SO4
25g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) carry out reacting (reaction temperature 25
DEG C, 2 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt and calciner gas (CO2
Concentration 75%) reaction (reaction temperature 25 DEG C, 2 hours response time) obtain 1000m3Reactant liquor (contains
There is Na2SO4 25g/l、NaCl 283g/l、Na2CO3 2.65g/l、Ca2SO43.0g/l)；1000m3
Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C, 6 hours response time) generation carbon containing
Acid calcium (CaCO3) suspension that precipitates；This suspension of solid-liquid separation respectively obtains 2.205 tons of calcium carbonate (CaCO3)
Precipitate, 1000m3Mother solution is (containing Na2SO428.1g/l、NaCl 283g/l).2.205 ton carbonic acid
Ca-deposit fresh water washing (wash temperature 25 DEG C) solid-liquid separation afterwards obtains 2.205 tons and washes rear calcium carbonate
(CaCO3) and cleaning mixture (containing a small amount of Na2SO4、NaCl)；Wash rear calcium carbonate for 2.205 tons (to do through being dried
Dry temperature 140 DEG C) obtain 2.205 tons of product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaCl)
Produce waste water with other to be mixed for dissolving raw ore (sulfur acid sodium, sodium chloride, sodium hydroxide, calcium sulfate etc.
Composition).
Embodiment 2: take 1600m3Calciner gas (CO2Concentration 75%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) react
(reaction temperature 25 DEG C, 2 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt with
Calciner gas (CO2Concentration 75%) reaction (reaction temperature 25 DEG C, 2 hours response time) obtain 1000m3
Reactant liquor is (containing Na2SO4 25g/l、NaNO3 100g/l、NaCl 283g/l、Na2CO3 2.65g/l、
Ca2SO43.0g/l)；1000m3Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C,
6 hours response time) produce containing calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation
Liquid respectively obtains 2.205 tons of calcium carbonate (CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、
NaNO3100g/l、NaCl 283g/l).2.205 tons of lime deposit fresh water wash (wash temperature
25 DEG C) afterwards solid-liquid separation obtain 2.205 tons and wash rear calcium carbonate (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、
NaNO3、NaCl)；Wash rear calcium carbonate for 2.205 tons and obtain 2.205 through being dried (baking temperature 140 DEG C)
Ton product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaNO3, NaCl) with other produce waste water mix
For dissolving raw ore (containing compositions such as sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, calcium sulfate).
Embodiment 3: take 1600m3Calciner gas (CO2Concentration 75%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaOH 2.0g/l、Ca2SO43.0g/l) carry out reacting (reaction temperature 25
DEG C, 2 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt and calciner gas (CO2
Concentration 75%) reaction (reaction temperature 25 DEG C, 2 hours response time) obtain 1000m3Reactant liquor (contains
There is Na2SO4 25g/l、NaNO3 100g/l、Na2CO3 2.65g/l、Ca2SO43.0g/l)；1000m3
Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C, 6 hours response time) generation and contain
Calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation respectively obtains 2.205 tons of calcium carbonate
(CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、NaNO3 100g/l)。2.205
Ton lime deposit fresh water washing (wash temperature 25 DEG C) solid-liquid separation afterwards obtains 2.205 tons and washes rear carbon
Acid calcium (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、NaNO3、NaCl)；Wash rear carbonic acid for 2.205 tons
Calcium obtains 2.205 tons of product calcium carbonate through being dried (baking temperature 140 DEG C)；Cleaning mixture is (containing a small amount of
Na2SO4、NaNO3, NaCl) with other produce waste water be mixed for dissolve raw ore (containing sodium sulfate, chlorination
The compositions such as sodium, sodium nitrate, sodium hydroxide, calcium sulfate).
Embodiment 4: take 1600m3Calciner gas (CO2Concentration 70%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) react
(reaction temperature 35 DEG C, 8 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt with
Calciner gas (CO2Concentration 70%) reaction (reaction temperature 35 DEG C, 8 hours response time) obtain 1000m3
Reactant liquor is (containing Na2SO4 25g/l、NaNO3 100g/l、NaCl 283g/l、Na2CO3 2.65g/l、
Ca2SO43.0g/l)；1000m3Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C,
6 hours response time) produce containing calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation
Liquid respectively obtains 2.205 tons of calcium carbonate (CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、
NaNO3100g/l、NaCl 283g/l).2.205 tons of lime deposit fresh water wash (wash temperature
20 DEG C) afterwards solid-liquid separation obtain 2.205 tons and wash rear calcium carbonate (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、
NaNO3、NaCl)；Wash rear calcium carbonate for 2.205 tons and obtain 2.205 through being dried (baking temperature 140 DEG C)
Ton product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaNO3, NaCl) with other produce waste water mix
For dissolving raw ore (containing compositions such as sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, calcium sulfate).
Embodiment 5: take 1600m3Calciner gas (CO2Concentration 80%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) react
(reaction temperature 25 DEG C, 2 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt with
Calciner gas (CO2Concentration 80%) reaction (reaction temperature 25 DEG C, 2 hours response time) obtain 1000m3
Reactant liquor is (containing Na2SO4 25g/l、NaNO3 100g/l、NaCl 283g/l、Na2CO3 2.65g/l、
Ca2SO43.0g/l)；1000m3Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C,
6 hours response time) produce containing calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation
Liquid respectively obtains 2.205 tons of calcium carbonate (CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、
NaNO3100g/l、NaCl 283g/l).2.205 tons of lime deposit fresh water wash (wash temperature
45 DEG C) afterwards solid-liquid separation obtain 2.205 tons and wash rear calcium carbonate (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、
NaNO3、NaCl)；Wash rear calcium carbonate for 2.205 tons and obtain 2.205 through being dried (baking temperature 120 DEG C)
Ton product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaNO3, NaCl) with other produce waste water mix
For dissolving raw ore (containing compositions such as sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, calcium sulfate).
Embodiment 6: take 1600m3Calciner gas (CO2Concentration 75%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) react
(reaction temperature 45 DEG C, 6 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt with
Calciner gas (CO2Concentration 75%) reaction (reaction temperature 45 DEG C, 6 hours response time) obtain 1000m3
Reactant liquor is (containing Na2SO4 25g/l、NaNO3 100g/l、NaCl 283g/l、Na2CO3 2.65g/l、
Ca2SO43.0g/l)；1000m3Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C,
6 hours response time) produce containing calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation
Liquid respectively obtains 2.205 tons of calcium carbonate (CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、
NaNO3100g/l、NaCl 283g/l).2.205 tons of lime deposit fresh water wash (wash temperature
55 DEG C) afterwards solid-liquid separation obtain 2.205 tons and wash rear calcium carbonate (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、
NaNO3、NaCl)；2.205 ton washes rear calcium carbonate obtains 2.205 through being dried (baking temperature 130 DEG C)
Ton product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaNO3, NaCl) with other produce waste water mix
For dissolving raw ore (containing compositions such as sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, calcium sulfate).
Embodiment 7: take 1600m3Calciner gas (CO2Concentration 75%) and 1000m3Salt is (containing Na2SO4
25g/l、NaNO3 100g/l、NaCl 283g/l、NaOH 2.0g/l、Ca2SO43.0g/l) react
(reaction temperature 55 DEG C, 5 hours response time), the sodium hydroxide (NaOH 2.0g/l) in salt with
Calciner gas (CO2Concentration 75%) reaction (reaction temperature 55 DEG C, 5 hours response time) obtain 1000m3
Reactant liquor is (containing Na2SO4 25g/l、NaNO3 100g/l、NaCl 283g/l、Na2CO3 2.65g/l、
Ca2SO43.0g/l)；1000m3Sodium carbonate in reactant liquor and calcium sulfate react (reaction temperature 25 DEG C,
6 hours response time) produce containing calcium carbonate (CaCO3) sedimentary suspension；This suspension of solid-liquid separation
Liquid respectively obtains 2.205 tons of calcium carbonate (CaCO3) precipitate, 1000m3Mother solution is (containing Na2SO4 28.1g/l、
NaNO3100g/l、NaCl 283g/l).2.205 tons of lime deposit fresh water wash (wash temperature
65 DEG C) afterwards solid-liquid separation obtain 2.205 tons and wash rear calcium carbonate (CaCO3) and cleaning mixture (containing a small amount of Na2SO4、
NaNO3、NaCl)；Wash rear calcium carbonate for 2.205 tons and obtain 2.205 through being dried (baking temperature 160 DEG C)
Ton product calcium carbonate；Cleaning mixture is (containing a small amount of Na2SO4、NaNO3, NaCl) with other produce waste water mix
For dissolving raw ore (containing compositions such as sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide, calcium sulfate).
Claims (6)
1. a calciner gas produces calcium carbonate technique with calcium sulfate, it is characterised in that: it includes following step
Rapid:
A. soda calcining furnace produce calciner gas with containing sodium sulfate, sodium chloride, sodium nitrate, sodium hydroxide,
The salt of calcium sulfate, reacts 2-8 hour at 25-60 DEG C, obtains reactant liquor, in this reactant liquor after reaction
Containing sodium sulfate, sodium chloride, sodium nitrate, sodium carbonate, calcium sulfate；
B. the sodium carbonate in this reactant liquor and calcium sulfate react 2-8 hour at 25-60 DEG C, and reaction generation contains
The suspension of precipitation of calcium carbonate；
C. this suspension of solid-liquid separation, respectively obtains lime deposit and mother solution；
D. being washed with fresh water by this lime deposit, wash temperature is 20-90 DEG C, and solid-liquid separation obtains
Wash rear calcium carbonate and cleaning mixture；
E. this is washed rear calcium carbonate and be dried to obtain product calcium carbonate through 120-160 DEG C；
F. this cleaning mixture with produce waste water mix with dissolving sulfur acid sodium, sodium chloride, sodium nitrate, sodium hydroxide,
The raw ore of calcium sulfate.
Calciner gas the most according to claim 1 produces calcium carbonate technique with calcium sulfate, and its feature exists
In: the CO in described calciner gas2Concentration is 70-80%.
Calciner gas the most according to claim 1 produces calcium carbonate technique with calcium sulfate, and its feature exists
In: in described salt, the content of each component is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、NaCl
5-320g/l、NaOH 0.2-10.0g/l、Ca2SO4 0.3-7.0g/l。
Calciner gas the most according to claim 1 produces calcium carbonate technique with calcium sulfate, and its feature exists
In: in described reactant liquor, each composition weight content is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、
NaCl 5-320g/l、Na2CO3 0.27-13.25g/l、Ca2SO4 0.3-7.0g/l。
Calciner gas the most according to claim 1 produces calcium carbonate technique with calcium sulfate, and its feature exists
In: in described mother solution, each composition weight content is: Na2SO4 0.3-330g/l、NaNO3 50-300g/l、NaCl
5-320g/l。
Calciner gas the most according to claim 1 produces calcium carbonate technique with calcium sulfate, and its feature exists
In: described production waste water is the mother solution in described step C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023054239A1 (en) * | 2021-09-30 | 2023-04-06 | 住友大阪セメント株式会社 | Method for fixing carbon dioxide, method for producing calcium carbonate, and method for utilizing waste gypsum board |
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| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN103570041A (en) * | 2012-08-06 | 2014-02-12 | 中国中轻国际工程有限公司 | Purification process for brine with high sodium sulphate content |
| CN103663529A (en) * | 2012-04-28 | 2014-03-26 | 浙江大学 | Method for preparing nano-calcium carbonate slurry by using waste gypsum as calcium source, product and application |
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| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN103663529A (en) * | 2012-04-28 | 2014-03-26 | 浙江大学 | Method for preparing nano-calcium carbonate slurry by using waste gypsum as calcium source, product and application |
| CN103570041A (en) * | 2012-08-06 | 2014-02-12 | 中国中轻国际工程有限公司 | Purification process for brine with high sodium sulphate content |
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| WO2023054239A1 (en) * | 2021-09-30 | 2023-04-06 | 住友大阪セメント株式会社 | Method for fixing carbon dioxide, method for producing calcium carbonate, and method for utilizing waste gypsum board |
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