CN109809442B - System and method for producing magnesium hydroxide and light calcium carbonate by purifying ash in calcium carbide furnace - Google Patents
System and method for producing magnesium hydroxide and light calcium carbonate by purifying ash in calcium carbide furnace Download PDFInfo
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- CN109809442B CN109809442B CN201811628620.4A CN201811628620A CN109809442B CN 109809442 B CN109809442 B CN 109809442B CN 201811628620 A CN201811628620 A CN 201811628620A CN 109809442 B CN109809442 B CN 109809442B
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 82
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 44
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 43
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 43
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 41
- 239000005997 Calcium carbide Substances 0.000 title claims abstract description 26
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 50
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- 239000002893 slag Substances 0.000 claims abstract description 42
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 25
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract 2
- 230000008018 melting Effects 0.000 claims abstract 2
- 239000012452 mother liquor Substances 0.000 claims description 62
- 239000012065 filter cake Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical group ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a system and a method for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace, wherein a discharge port of a slag dissolving reactor is connected with a feed port of a first filter; the liquid phase discharge port of the first filter is connected with the first feed port of the magnesium precipitation reactor; the discharge port of the magnesium precipitation reactor is connected with the feed port of the second filter; the liquid phase discharge port of the second filter is connected with the first feed port of the calcium precipitation reactor; the discharge port of the calcium precipitation reactor is connected with the feed port of the third filter; the liquid phase discharge port of the third filter is connected with the feed port of the ammonia still; the discharge port of the ammonia still is connected with the feed port of the evaporation concentration tower; the discharge port of the evaporation concentration tower is connected with the feed port of the cooling crystallization tower; the discharge port of the cooling crystallization tower is connected with the feed port of the fourth filter; the liquid phase discharge port of the fourth filter is connected with the fifth feed port of the slag melting reactor. The system converts the purified ash into magnesium hydroxide and calcium carbonate, realizes the utilization of the purified ash, and reduces the discharge amount of waste residues.
Description
Technical Field
The invention belongs to the technical field of recycling of purified ash of a calcium carbide furnace, and particularly relates to a system and a method for producing magnesium hydroxide and light calcium carbonate from the purified ash of the calcium carbide furnace.
Background
In the production process of calcium carbide, the purified ash generated after the purification of the tail gas of calcium carbide is burned by a fluidized bed furnace, and the gray spherical waste residue generated after the burning of the tail gas of calcium carbide is commonly called purified ash. The main components of the ash are magnesia and calcium oxide, wherein the mass fraction of the magnesia can reach 40-50%, and the mass fraction of the calcium oxide can reach 30%. The existing general treatment method for purifying ash is to use the ash to be buried after being transported outside, so that dust pollution is generated in the transportation process, and the land is occupied. In addition, magnesium products such as magnesium hydroxide, magnesium oxide and the like are mostly produced from ores such as dolomite, serpentine, magnesite and the like, and light calcium carbonate is produced from ores such as limestone and the like, so that the ecological environment is damaged due to mass exploitation.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a system and a method for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace, which not only can solve the problem of solid waste residue emission in calcium carbide production, but also can change waste into valuable and protect ecological environment.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a system for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace comprises an acid storage tank, an ash feeder, an oxidant tank, an ammonia storage tank, a slag dissolving reactor, a first filter, a magnesium precipitation reactor, a second filter, a carbon source tank, a calcium precipitation reactor, a third filter, an ammonia distillation tower, an evaporation concentration tower, a cooling crystallization tower and a fourth filter; the slag dissolving reactor comprises five feed inlets, the acid storage tank is connected with the first feed inlet of the slag dissolving reactor, the ash feeder is connected with the second feed inlet of the slag dissolving reactor, the oxidant tank is connected with the third feed inlet of the slag dissolving reactor, and the first discharge outlet of the ammonia storage tank is connected with the fourth feed inlet of the slag dissolving reactor; the discharge port of the slag dissolving reactor is connected with the feed port of the first filter; the liquid phase discharge port of the first filter is connected with the first feed port of the magnesium precipitation reactor; the second discharge port of the ammonia storage tank is connected with the second feed port of the magnesium precipitation reactor; the discharge port of the magnesium precipitation reactor is connected with the feed port of the second filter; the liquid phase discharge port of the second filter is connected with the first feed port of the calcium precipitation reactor; the carbon source tank is connected with a second feed inlet of the calcium precipitation reactor; the discharge port of the calcium precipitation reactor is connected with the feed port of the third filter; the liquid phase discharge port of the third filter is connected with the feed port of the ammonia still; the discharge port of the ammonia still is connected with the feed port of the evaporation concentration tower; the discharge port of the evaporation concentration tower is connected with the feed port of the cooling crystallization tower; the discharge port of the cooling crystallization tower is connected with the feed port of the fourth filter; the liquid phase discharge port of the fourth filter is connected with the fifth feed port of the slag-soluble reactor.
A method for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace comprises the following steps:
(1) Acid and purified ash are reacted in a slag dissolving reactor, fourth mother liquor is introduced for full mixing, ammonia is added at the temperature of 30-90 ℃, the pH value is regulated to 6-7, an oxidant is added, a first filter is used for filtering and separating after the reaction is finished to obtain first mother liquor and a waste residue filter cake, the waste residue filter cake is washed to obtain waste residue, and the washing filtrate is combined with the first mother liquor;
(2) The first mother liquor enters a magnesium precipitation reactor, ammonia is continuously added at the temperature of 30-90 ℃, after the reaction is finished, the mixture is kept stand, then the mixture enters a second filter for filtering and separating to obtain a second mother liquor and a magnesium hydroxide filter cake, the second mother liquor and the magnesium hydroxide filter cake are washed and dried to obtain magnesium hydroxide, and the water washing filtrate is mixed with the second mother liquor;
(3) The second mother liquor enters a calcium precipitation reactor, a carbon source is added at the temperature of 30-90 ℃, after the reaction is finished, the mixture is kept stand, then enters a third filter for filtration and separation to obtain a third mother liquor and a light calcium carbonate filter cake, the light calcium carbonate filter cake is obtained after washing and drying, and the washing filtrate is merged into the third mother liquor;
(4) The third mother liquor enters an ammonia distillation tower for ammonia distillation, enters an evaporation concentration tower, enters a cooling crystallization tower for crystallization, enters a fourth filter for filtration and separation to obtain a fourth mother liquor and an ammonium chloride filter cake, and is dried to obtain ammonium chloride; and returning the fourth mother liquor to the slag dissolving reactor for circulation.
Preferably, the acid in step (1) is hydrochloric acid or nitric acid, and the molar concentration thereof is 1-12 mol/L.
Preferably, the acid and the cleaned ash in step (1) are added in a ratio of 35 to 50 moles of acid to dissolve 1kg of cleaned ash.
Preferably, the oxidant in the step (1) is hypochlorous acid, sodium hypochlorite or calcium hypochlorite, and the addition amount of the oxidant is 0.001-0.05 kg of available chlorine per kg of ash.
Preferably, the ammonia in step (1) is ammonia gas or aqueous ammonia.
More preferably, the mass concentration of the aqueous ammonia is 5 to 25%.
Preferably, the reaction time after the oxidant is added in the step (1) is 10 to 90 minutes.
Preferably, the washing water amount of the waste residue filter cake in the step (1) is 0.2-2 times of the mass of the wet filter residue.
Preferably, the reaction temperature in steps (1) to (3) is 30 to 90 ℃.
Preferably, the reaction time in the step (2) is 0.5 to 3 hours, and the standing time is 0.5 to 3 hours.
Preferably, the molar ratio of ammonia to magnesium ions in step (2) is 2-5:1.
Preferably, the washing water amount of the magnesium hydroxide filter cake in the step (2) is 0.5-4 times of the mass of the wet filter cake.
Preferably, the carbon source in step (3) is CO 2 Or ammonium bicarbonate.
Preferably, the molar ratio of the carbon source to the calcium ions in the second mother liquor in step (3) is 0.85-0.95: 1.
preferably, the reaction time in the step (3) is 0.5 to 3 hours, and the standing time is 0.5 to 3 hours.
Preferably, the washing water amount of the light calcium carbonate filter cake in the step (3) is 0.5-4 times of the mass of the wet filter cake.
Preferably, step (4) employs two-stage or three-stage high-efficiency evaporation.
Preferably, the fourth mother liquor after crystallization in the step (4) is returned to the slag reactor for circulation.
In the invention, the specific reaction and action of each step are as follows:
(1) The purified ash is mainly composed of magnesium oxide and calcium oxide (accounting for about 80%), and further contains impurities such as silicon oxide, potassium oxide, sodium oxide, aluminum oxide, ferric oxide, manganese oxide and the like. The acid reacts with the purified ash to generate soluble salt, and ammonia is added to adjust the pH value to generate hydroxide precipitate from metal ions such as aluminum, iron and the like. The divalent manganese ion cannot form a precipitate when the pH=6-7, and the divalent manganese ion can be oxidized to form tetravalent manganese ion by adding an oxidant, and the tetravalent manganese ion is unstable and usually takes MnO as a common material 2 The precipitate is separated out, and various impurities in the solution can be removed by filtration.
Mn 2+ +ClO-+2OH-→MnO 2 +Cl-+H 2 O
(2) Under alkaline condition, magnesium ions and hydroxide can generate magnesium hydroxide sediment, magnesium hydroxide can be obtained by filtration, calcium ions and hydroxide can react with ammonium bicarbonate to generate calcium carbonate sediment, and light calcium carbonate can be obtained by filtration.
Mg 2+ +2OH-→Mg(OH) 2 ↓
Ca 2+ +HCO 3 - +OH - →CaCO 3 ↓+H 2 O
The system and the method for producing the magnesium hydroxide and the light calcium carbonate by purifying ash in the calcium carbide furnace have the following beneficial effects:
at present, the purified ash is generally treated by a landfill method, which not only wastes resources, but also pollutes the environment. The system and the method convert the purified ash into magnesium hydroxide and calcium carbonate, realize the resource utilization of the purified ash, reduce the discharge amount of waste residues, change waste into valuable, protect the environment and have certain economic benefit.
The system and the method adopt a chemical precipitation method to realize the separation of calcium and magnesium, realize the combined production of magnesium hydroxide and light calcium carbonate, and have stable production, less equipment and less investment.
The system and the method recycle the generated waste liquid (namely the fourth mother liquid), and finally the whole system has no waste water discharge, thereby realizing the clean conversion and utilization of chemical waste residues.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention, and that other related drawings can be obtained according to these drawings without inventive effort for a person skilled in the art, since they should not be considered as limiting the scope.
Fig. 1 is a schematic diagram of a system for producing magnesium hydroxide and light calcium carbonate from ash residue purified by a calcium carbide furnace according to an embodiment of the invention.
Reference numerals: 1-an acid storage tank; 2-ash feeders; a 3-oxidant tank; 4-an ammonia storage tank; a 5-slag dissolution reactor; 6-a first filter; 7-a magnesium separation reactor; 8-a second filter; 9-a calcium precipitation reactor; 10-a third filter; 11-an ammonia still; 12-evaporating and concentrating tower; 13-cooling a crystallization tower; 14-a fourth filter; 15-a carbon source tank; 41-a first discharge port of the ammonia storage tank; 42-a second discharge port of the ammonia storage tank; 51-a first feed inlet of the slag dissolving reactor; 52-a second feed inlet of the slag dissolving reactor; 53-a third feed inlet of the slag dissolving reactor; 54-a fourth feed inlet of the slag dissolving reactor; 55-a fifth feed inlet of the slag dissolving reactor; 71-a first feed inlet of the magnesium precipitation reactor; 72-a second feed inlet of the magnesium precipitation reactor; 91-a first feed inlet of a calcium precipitation reactor; 92-a second feed inlet of the calcium precipitation reactor.
Detailed Description
The technical scheme of the present invention will be clearly and completely described in the following examples.
TABLE 1 composition and content of purified ash
Example 1
As shown in fig. 1, the present embodiment provides a system for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace, which comprises an acid storage tank 1, an ash feeder 2, an oxidant tank 3, an ammonia storage tank 4, a slag dissolution reactor 5, a first filter 6, a magnesium precipitation reactor 7, a second filter 8, a carbon source tank 14, a calcium precipitation reactor 9, a third filter 10, an ammonia still 11, an evaporation concentration tower 12, a cooling crystallization tower 13 and a fourth filter 15.
The slag dissolving reactor 5 comprises five feed inlets, namely a first feed inlet 51, a second feed inlet 52, a third feed inlet 53, a fourth feed inlet 54 and a fifth feed inlet 55, acid is added from the acid storage tank 1 through the first feed inlet 51, purified ash enters from the ash feeder 2 through the second feed inlet 52, after complete dissolution, fourth mother liquor is introduced from the fifth feed inlet 55, after complete mixing, ammonia is added from the ammonia storage tank 4 through the fourth feed inlet 54 to adjust the pH value, then oxidant is added from the oxidant tank 3 through the third feed inlet 53, and after complete reaction, the first mother liquor is obtained after filtering and washing by the first filter 6.
The first mother liquor enters the magnesium precipitation reactor 7 through the first feed inlet 71, ammonia enters the magnesium precipitation reactor 7 through the second feed inlet 72 from the second discharge outlet 41 of the ammonia storage tank, and after the reaction is completed, the ammonia enters the second filter 8 for filtering and washing, thus obtaining the second mother liquor.
The second mother liquor enters the calcium precipitation reactor 9 through the first feed inlet 91, the carbon source enters the calcium precipitation reactor 9 from the carbon source tank 15 through the second feed inlet 92, and the third mother liquor is obtained after the reaction is completed and enters the third filter 10 for filtration and washing.
The third mother liquor enters an ammonia distillation tower 11 for ammonia removal, enters an evaporation concentration tower 12, and enters a fourth filter 14 for filtration after being crystallized in a cooling crystallization tower 13, so as to obtain a fourth mother liquor. The fourth mother liquor is circulated from the fifth feed inlet 55 into the slag reactor 5.
The embodiment also provides a method for producing magnesium hydroxide and light calcium carbonate by purifying ash in a calcium carbide furnace, which comprises the following steps:
(1) Adding 3L of hydrochloric acid with the concentration of 12mol/L into a reactor, adding 1kg of purified ash, introducing a fourth mother solution after dissolution, adjusting the temperature to 50+/-2 ℃, introducing ammonia gas to adjust the pH value to 6, then adding 0.1kg of calcium hypochlorite (with the effective chlorine content of 30%) to react for 60min, filtering after the reaction is finished to obtain a first mother solution and a waste residue filter cake, washing the waste residue filter cake with equal mass to obtain 0.35kg of waste residue, and mixing the washing filtrate with the first mother solution;
(2) The first mother liquor enters a magnesium precipitation reactor, ammonia is continuously added at 50+/-2 ℃, the molar ratio of the added ammonia amount to magnesium ions is 3:1, the reaction is carried out for 3 hours, the reaction is carried out for 2 hours, then the reaction product enters a second filter for filtering and separating to obtain a second mother liquor and a magnesium hydroxide filter cake, water washing with 2 times of the mass of wet filter residues is carried out to obtain 0.52kg of magnesium hydroxide, and the water washing filtrate is merged into the second mother liquor;
(3) The second mother solution enters a calcium precipitation reactor and is introduced with CO at 50+/-2 DEG C 2 ，CO 2 The molar ratio of calcium ions in the second mother liquor was 0.85:1, reacting for 3 hours, standing for 1 hour, then filtering and separating by a third filter to obtain a third mother liquor and a light calcium carbonate filter cake, washing with water with the mass 2 times that of wet filter residues to obtain 0.43kg of light calcium carbonate, and mixing the water washing filtrate with the third mother liquor;
(4) The third mother liquor enters an ammonia distillation tower for ammonia distillation, enters a triple-effect evaporation concentration tower, enters a cooling crystallization tower for crystallization, enters a fourth filter for filtration and separation to obtain a fourth mother liquor and an ammonium chloride filter cake, and is dried to obtain 1.5kg of ammonium chloride; and returning the fourth mother liquor to the slag reactor for circulation.
In the embodiment, the recovery rate of the magnesium hydroxide can reach 73.0%, the purity of the product can reach 99.0%, the recovery rate of the light calcium carbonate can reach 81.6%, and the purity of the product can reach 98.0%.
Example 2
Unlike example 1, this example provides a method for producing magnesium hydroxide and light calcium carbonate from ash of calcium carbide furnace purification, comprising:
(1) Adding 4.5L of 9mol/L hydrochloric acid into a reactor, adding 1kg of purified ash, introducing a fourth mother solution after dissolution, adjusting the temperature to 60+/-2 ℃, introducing 20% ammonia water to adjust the pH to 6, then adding 0.05kg of calcium hypochlorite (the effective chlorine content is 30%) to react for 10min, filtering after the reaction is finished to obtain a first mother solution and a waste residue filter cake, washing the waste residue filter cake with equal mass to obtain 0.3kg of waste residue, and mixing the washing filtrate with the first mother solution;
(2) The first mother liquor enters a magnesium precipitation reactor, 20% ammonia water is continuously added at 60+/-2 ℃, the molar ratio of the ammonia amount to magnesium ions is 5:1, the reaction is carried out for 1h, the reaction is carried out for 2h, then the reaction product enters a second filter for filtering and separating to obtain a second mother liquor and a magnesium hydroxide filter cake, water washing with 4 times of the mass of wet filter residues is carried out to obtain 0.55kg of magnesium hydroxide, and the water washing filtrate is merged into the second mother liquor;
(3) The second mother solution enters a calcium precipitation reactor, ammonium bicarbonate is added at 60+/-2 ℃, and the molar ratio of the ammonium bicarbonate to calcium ions in the second mother solution is 0.9:1, reacting for 1h, standing for 2h, then filtering and separating by a third filter to obtain a third mother liquor and a light calcium carbonate filter cake, washing with water with the mass 1 time of that of the wet filter residue to obtain 0.45kg of light calcium carbonate, and mixing the water washing filtrate with the third mother liquor;
(4) The third mother liquor enters an ammonia distillation tower for ammonia distillation, enters a triple-effect evaporation concentration tower, enters a cooling crystallization tower for crystallization, enters a fourth filter for filtration and separation to obtain a fourth mother liquor and an ammonium chloride filter cake, and is dried to obtain 1.6kg of ammonium chloride; and returning the fourth mother liquor to the slag reactor for circulation.
In the embodiment, the recovery rate of the magnesium hydroxide can reach 77.2%, the purity of the product can reach 98.5%, the recovery rate of the light calcium carbonate can reach 85.4%, and the purity of the product can reach 98.0%.
Example 3
Unlike example 2, this example provides a method for producing magnesium hydroxide and light calcium carbonate from ash of calcium carbide furnace purification, comprising:
(1) Adding 50L of hydrochloric acid with the concentration of 1mol/L into a reactor, adding 1kg of purified ash, introducing a fourth mother solution after dissolution, adjusting the temperature to 90+/-2 ℃, introducing 5% ammonia water to adjust the pH value to 7, then adding 0.5kg of sodium hypochlorite solution (the effective chlorine content is 10%) for reacting for 90min, filtering after the reaction is finished to obtain a first mother solution and a waste residue filter cake, washing the waste residue filter cake with water with the same mass to obtain 0.2kg of waste residue, and mixing the filtrate with the first mother solution;
(2) The first mother liquor enters a magnesium precipitation reactor, 5% ammonia water is continuously added at 80+/-2 ℃, the molar ratio of the ammonia amount to magnesium ions is 2:1, the reaction is carried out for 2 hours, the reaction is carried out for 3 hours, then the reaction product enters a second filter for filtration and separation to obtain a second mother liquor and a magnesium hydroxide filter cake, 0.5 time of water washing with the mass of wet filter residue is used for obtaining 0.50kg of magnesium hydroxide, and the water washing filtrate is merged into the second mother liquor;
(3) The second mother solution enters a calcium precipitation reactor, ammonium bicarbonate is added at 80+/-2 ℃, and the molar ratio of the ammonium bicarbonate to calcium ions in the second mother solution is 0.95:1, reacting for 2 hours, standing for 3 hours, then filtering and separating by a third filter to obtain a third mother solution and a light calcium carbonate filter cake, washing with water with the mass of 0.5 times that of the wet filter residue to obtain 0.45kg of light calcium carbonate, and merging the water washing filtrate into the third mother solution;
(4) The third mother liquor enters an ammonia distillation tower for ammonia distillation, enters a triple-effect evaporation concentration tower, enters a cooling crystallization tower for crystallization, enters a fourth filter for filtration and separation to obtain a fourth mother liquor and an ammonium chloride filter cake, and is dried to obtain 1.3kg of ammonium chloride; and returning the fourth mother liquor to the slag reactor for circulation.
In the embodiment, the recovery rate of the magnesium hydroxide can reach 70.2%, the purity of the product can reach 98.0%, the recovery rate of the light calcium carbonate can reach 85.4%, and the purity of the product can reach 98.0%.
The above description is only a preferred embodiment of the present invention, and the patent protection claims are not limited thereto, but all equivalent structural changes made by the specification and the attached drawings are included in the protection scope of the present invention.
Claims (7)
1. The method for producing magnesium hydroxide and light calcium carbonate by using the calcium carbide furnace purified ash slag is characterized by specifically adopting a system for producing magnesium hydroxide and light calcium carbonate by using the calcium carbide furnace purified ash slag, wherein the system comprises an acid storage tank (1), an ash slag feeder (2), an oxidant tank (3), an ammonia storage tank (4), a dissolved slag reactor (5), a first filter (6), a magnesium precipitation reactor (7), a second filter (8), a calcium precipitation reactor (9), a third filter (10), an ammonia distillation tower (11), an evaporation concentration tower (12), a cooling crystallization tower (13), a fourth filter (14) and a carbon source tank (15), wherein the method comprises the following steps:
the discharge port of the slag dissolving reactor (5) is connected with the feed port of the first filter (6); the liquid phase discharge port of the first filter (6) is connected with the first feed port of the magnesium precipitation reactor (7); the discharge port of the magnesium precipitation reactor (7) is connected with the feed port of the second filter (8); the liquid phase discharge port of the second filter (8) is connected with the first feed port of the calcium precipitation reactor (9); the discharge port of the calcium precipitation reactor (9) is connected with the feed port of the third filter (10); the liquid phase discharge port of the third filter (10) is connected with the feed port of the ammonia still (11); the discharge port of the ammonia distillation tower (11) is connected with the feed port of the evaporation concentration tower (12); the discharge port of the evaporation concentration tower (12) is connected with the feed port of the cooling crystallization tower (13); the discharge port of the cooling crystallization tower (13) is connected with the feed port of the fourth filter (14); the liquid phase discharge port of the fourth filter (14) is connected with a fifth feed port (55) of the slag melting reactor;
the slag reactor (5) is further provided with a first slag reactor feed port (51), a second slag reactor feed port (52), a third slag reactor feed port (53) and a fourth slag reactor feed port (54), wherein the first slag reactor feed port (51) is connected with a discharge port of the acid storage tank (1), the second slag reactor feed port (52) is connected with a discharge port of the ash feeder (2), the third slag reactor feed port (53) is connected with a discharge port of the oxidant tank (3), and the fourth slag reactor feed port (54) is connected with a first discharge port (41) of the ammonia storage tank (4);
the magnesium precipitation reactor (7) is connected with a second discharge port (42) of an ammonia storage tank of the ammonia storage tank (4) through a second feed port (72) of the magnesium precipitation reactor arranged on the magnesium precipitation reactor, and the calcium precipitation reactor (9) is connected with a discharge port of a carbon source tank (15) through a second feed port (92) of the calcium precipitation reactor arranged on the calcium precipitation reactor;
the specific method comprises the following steps: acid and purified ash are reacted in a slag dissolving reactor (5), fourth mother liquor is introduced for full mixing, ammonia is added at the temperature of 30-90 ℃, the pH value is regulated to 6-7, then an oxidant is added, the mixture enters a first filter (6) for filtering and separating after the reaction is finished to obtain first mother liquor and a waste residue filter cake, the waste residue filter cake is washed to obtain waste residue and washing filtrate, and the washing filtrate is combined with the first mother liquor; the first mother liquor enters a magnesium precipitation reactor (7), ammonia is continuously added at the temperature of 30-90 ℃, after the reaction is finished, the mixture is kept stand for 1-3 hours, then the mixture enters a second filter (8) for filtering and separating to obtain a second mother liquor and a magnesium hydroxide filter cake, the second mother liquor and the magnesium hydroxide filter cake are washed and dried to obtain magnesium hydroxide, and the washing filtrate is merged into the second mother liquor; the second mother liquor enters a calcium precipitation reactor (9), a carbon source is added at the temperature of 30-90 ℃, after the reaction is finished, the mixture is stood for 1-3 hours, then enters a third filter (10) for filtering and separating to obtain a third mother liquor and a light calcium carbonate filter cake, the light calcium carbonate filter cake is obtained after washing and drying, and the water washing filtrate is merged into the third mother liquor; the third mother liquor enters an ammonia distillation tower (11) for ammonia distillation, enters an evaporation concentration tower (12), enters a cooling crystallization tower (13) for crystallization, enters a fourth filter (14) for filtration and separation to obtain a fourth mother liquor and an ammonium chloride filter cake, and is dried to obtain ammonium chloride; and returning the fourth mother liquor to the slag dissolving reactor for circulation.
2. The method for producing magnesium hydroxide and light calcium carbonate by using the purified ash of the calcium carbide furnace according to claim 1, wherein the acid is hydrochloric acid or nitric acid, and the molar concentration of the acid is 1-12 mol/L.
3. The method for producing magnesium hydroxide and light calcium carbonate from purified ash of calcium carbide furnace according to claim 1, wherein the acid and purified ash are added in the following ratio: 35-50 mol of acid dissolves 1kg of purified ash.
4. The method for producing magnesium hydroxide and light calcium carbonate by using ash purified by a calcium carbide furnace according to claim 1, wherein the oxidant is hypochlorous acid, sodium hypochlorite or calcium hypochlorite, and the adding amount of the oxidant is 0.001-0.05 kg of available chlorine per kg of ash.
5. The method for producing magnesium hydroxide and light calcium carbonate by using the calcium carbide furnace purified ash according to claim 1, wherein the ammonia is ammonia gas or ammonia water with a mass concentration of 5-25%.
6. The method for producing magnesium hydroxide and light calcium carbonate by using the calcium carbide furnace purified ash according to claim 1, wherein the carbon source is CO2 or ammonium bicarbonate, and the molar ratio of the carbon source to calcium ions in the second mother liquor is 0.85-0.95: 1.
7. the method for producing magnesium hydroxide and light calcium carbonate from ash purified by a calcium carbide furnace according to claim 1, wherein the fourth mother liquor is returned to the slag reactor for circulation.
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| US3980753A (en) * | 1970-02-20 | 1976-09-14 | Veitscher Magnesitwerke-Aktiengesellschaft | Industrial process of preparing magnesia of high purity |
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