CN103121717B - Method for preparing sodium chromate by mixing chromite and ferrochrome and device for method - Google Patents
Method for preparing sodium chromate by mixing chromite and ferrochrome and device for method Download PDFInfo
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- CN103121717B CN103121717B CN201310045109.2A CN201310045109A CN103121717B CN 103121717 B CN103121717 B CN 103121717B CN 201310045109 A CN201310045109 A CN 201310045109A CN 103121717 B CN103121717 B CN 103121717B
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Abstract
The invention discloses a method for preparing sodium chromate by mixing chromite and ferrochrome and a device for the method. The method comprises the following steps: measuring and mixing chromite and ferrochrome with sodium carbonate, sodium nitrate and sodium peroxide; pelleting the mixture with extracted liquid sodium chromate in a pelletizer; drying in a drier; returning part of the clinker to a flame kiln after the material is dried and cooled, so that chromite and ferrochrome are decomposed and oxidized in the form of fused liquid phase in molten salts so as to obtain the clinker of sodium chromate; and continuously soaking, filtering and cleaning after the clinker is cooled so that a chromium chemical primary product of liquid sodium chromate is obtained, wherein the flame kiln comprises a U-shaped kiln body, a partition wall and a low-position molten salt suction port, wherein the partition wall and the low-position molten salt suction port are arranged in the U-shaped kiln body; one or more blowing oxygen lances and one or more charging holes are arranged at the top of the kiln body, and a smoke outlet is arranged on the upper side of the kiln; and one or more oxygen lances are arranged at the bottom of the kiln. According to the method disclosed by the invention, the oxidation rate is as high as 98%, the clinker extraction rate is as high as 99.97%, and the chromium yield is 97.96%.
Description
Technical field
The present invention relates to the multiple mixing chromite of oxygen blast and ferrochrome at the bottom of a kind of tipburn oxygen blast and prepare method and the device thereof of Sodium chromate.
Background technology
Sodium dichromate with in national economy 15% range of goods relevant, one of inorganic salt principal item, be widely used in the aspects such as plating, tanning, printing and dyeing, medicine, feed, protective foods, aviation, pigment, catalyzer, oxygenant and metal inhibitor, be listed in one of competitive eight kinds of resource raw material product of most.The raw material of sodium dichromate mainly comes from the chromaking work primary products liquid Sodium chromate of chromite baked for producing.The sinter process of chromite is mainly divided into calcium roasting and calcium-free roasting.Their ultimate principle is all that chromite and soda ash are carried out oxidizing roasting under the high temperature conditions, makes the chromium in ore be converted into water miscible Sodium chromate.
Chromite is spinel magnetite type, its chemical composition more complicated, and researchers are basic with Cr
2o
3, Al
2o
3, Fe
2o
3, SiO
2, MgO, CaO, V
2o
5the research of assigning to of seven kinds of one-tenth and guides production.
Have calcium roasting owing to the addition of calcareous filler, bed drain purge is large, and sodium dichromate product per ton produces the quantity of slag more than 1.8 tons, Cr in slag
6+content generally about 0.7%, and contains carcinogens yellow ultramarine, serious environment pollution.Calcium-free roasting uses self-produced slag to return and makes filler, although reduce bed drain purge, in calcium-free roasting process, a large amount of return slag circulates in roasting system, and chromium oxidation rate is slow, have impact on chrome ore transformation efficiency.
Have calcium roasting to prepare Sodium chromate industrial making method to be: under calcium carbonate exists, by chromite and soda ash, Sodium chromate is prepared in roasting in the air of about 1000 DEG C.But partial sodium carbonate is also reacted rapidly with the gangue mineral of siliceous in furnace charge, aluminium and iron, generate the aluminosilicate of water glass, sodium aluminate, sodium ferrite or complexity, thus consume the higher soda ash of price more.Calcium carbonate plays two kinds of effects, and one is the vesicular structure being convenient to oxygen diffusion as form of bio-carrier, and two is be unlikely to be leached with the acidic oxide reaction in gangue composition as reagent, but obtains a small amount of yellow ultramarine carcinogens simultaneously.Chromite and sodium carbonate reaction mechanism more complicated, principal reaction formula is:
4FeO·Cr
2O
3+8Na
2CO
3+7O
2→8Na
2CrO
4+2Fe
2O
3+8CO
2(1)
Calcium-free roasting can avoid the above-mentioned shortcoming having calcium roasting, does not produce yellow ultramarine, though deslagging is few, sodium dichromate slag per ton still deslagging 0.7-0.8t, still reaches about 0.2% containing sexavalent chrome in slag.
During chromite calcium-free roasting chromite with soda ash and oxygen primitive reaction with have calcium identical.
What Chinese patent (Tianjin chemical research institute) CN85102681 and CN93112820.X related to is chromite powder and pellet calcium-free roasting, although this patent does not add calcareous filler when solving chromite roasting, ton sodium dichromate deslagging is low, but production efficiency is low, and kiln dross is serious.
Chinese patent (Chinese Academy Of Sciences Process Engineering Research Institute) applies for that CN98100556.X uses sodium hydroxide dissolved salt dielectric breakdown preparing sodium chromate from chromite, product leaches in high alkalinity district, although this method reduces temperature of reaction, it is high that the method joins alkali content, and equipment is corroded seriously, in gained chromium acid sodium alkaline liquid, free alkali is many, foreign matter content is high, and final treatment techniques is complicated, and magazins' layout was for up to tens of hours, therefore the production cost of the method is high, and industrialization difficulty is large.
What Bayer A.G two patent CN94117009.8 and US5667759 related to is that chromite prepares Sodium chromate without calcium oxygen enrichment, this method production efficiency comparatively in state-owned calcium method high 1.5 times, produce quantity of slag ton sodium dichromate less than 0.8 ton, but chromite comparatively high consumption, treatment of chromate slag still takes the removing toxic substances of wet method ferrous iron, dell landfill, easily pollutes environment.
Russia's chromite granulation calcium-free roasting patent RU2349552 (2009) adopts alkaline oxygenated reaction to use fine chrome mine, fine chrome mine and soda ash are levigate to granularity 0.05-0.06mm in advance, granular charge is made, not higher than 1100 DEG C of roasting 0.75-1.5h by the sodium hydroxide of concentration 200-400g/L and the SODIUMNITRATE (or nitrocalcite) of concentration 100-200g/L.Still there is performance dross problem in process of production in this method, causes industrialization difficulty large.
Russ P RU2096332C1 (1997) adopts low-temperature molten salt Sodium chromate chromic oxide iron ore, forms liquid phase main body, use pure oxygen in 1200 DEG C of reactions by a large amount of Sodium chromate circulation.This method and calcium-free roasting have similarity, and just recycle is without return slag, but Sodium chromate, be better than roasting method.Owing to only using theoretical amount alkali, therefore the side reaction of impurity greatly reduces, and water-soluble silicon in grog, aluminium are few, also there is not excess base Separation and Recovery problem, are better than caustic soda melting salt oxidation method.This method by-product scum, can fully utilize, but due to Sodium chromate usage quantity large, each ton of chromite transforms one ton of Sodium chromate, and need to return 4 tons of anhydrous sodium chromates, production efficiency is low, and Sodium chromate production cost is higher.
Chinese patent application (Sichuan Anxian Yinhe Constructional & Chemical Group Co., Ltd.) CN201110153036.X adopts chromite, soda ash (or sodium bicarbonate or sodium hydroxide), Sodium chromate (or sodium sulfate) three kinds or several granulation substantially, and be similar to fused solution phase oxidation roasting in refining lead bottom blowing furnace, and substantially reach continuous automatic production.This method is basic and Russ P RU2096332C1 is similar, although the minimum add-on of Sodium chromate is fallen very low, but when producing, in kiln, solid phase is more, when being less than the chromite of 4 times, due to by-product water glass easy during oxidation of chromite and more scum, cause fused salt viscosity higher, hinder oxidation of chromite, time serious, high viscosity fused salt can block oxygen rifle, cause stopping kiln maintenance, result is that Sodium chromate production cost raises.Meanwhile, existing defects in the structure of kiln, one is that raw material in kiln may because short circuit reason, and the residence time is too short and discharge, and causes oxidation ratio to decline; Another is that in kiln, two ends exist dead angle, and oxidizing reaction can be caused insufficient, and time serious, deposition affects discharging.Another is that end rifle, side rifle, end rifle are not considered to rob coordinated problem with burning, and this can cause cold oxygen directly to enter fused salt, because oxygen temperature is low, thus cause oxidation ratio to decline.
Therefore, prepare Sodium chromate for by chromite roasting, still need to solve and reduce furnace charge melt viscosity, boost productivity and reduce the problem of production cost.
Summary of the invention
Technical problem to be solved by this invention is to provide method and the device thereof that Sodium chromate prepared by a kind of mixing chromite and ferrochrome, solves the problems referred to above.
Technical problem to be solved by this invention is achieved through the following technical solutions:
A method for Sodium chromate prepared by mixing chromite and ferrochrome, it is characterized in that, is made up of following steps:
A () chromite and ferrochrome, mix after metering with soda ash, SODIUMNITRATE, sodium peroxide, by this compound, in granulating disc, rear liquid Sodium chromate carries out granulation with leaching;
The hot gas that b raw material that () forms particle are come by flame kiln in three rotary drum drying machines carries out drying;
C () dried particle raw material enter flame kiln together with melting grog after cooling, under oxygen or air exist, adopt mixing chromite and the ferrochrome of making of multiple oxygen blast at the bottom of tipburn oxygen blast to carry out decomposition oxidation in melting liquid phase in fused-salt medium, obtain sodium chromate chamotte;
D () grog, after the cooling of revolving cup high-pressure blast, uses hot water subsequent leaching in subsequent leaching groove;
E (), to the continuous filtration washing in filter of leaching slip, obtains chromaking work primary products liquid Sodium chromate.
The flue gas that described flame kiln is discharged and revolving cup high-pressure blast cool grog and by the air heated, enter waste heat recovery generating system.
The high scum that described (e) step is discharged enters smelts ferrochrome system.
Maturing temperature in described (c) step is 1510-1900 DEG C.
Maturing temperature in described (c) step is 1550-1650 DEG C.
In described compound, ferrochrome add total amount be the 0.01-100 of chromite quality doubly;
The total amount that adds of soda ash is that in raw material trivalent chromium is in the 1.2-3 of the quality of chromium sesquioxide doubly;
The total amount that adds of SODIUMNITRATE is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly;
In described compound, the total amount that adds of sodium peroxide is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly.
In described chromite, chromium content counts >=35wt% with chromium sesquioxide, and in ferrochrome, chromium content counts >=73wt% with chromium sesquioxide.
Wherein in compound during balling-up, in the liquid Sodium chromate added, Sodium chromate concentration is 200-500 grams per liter, its liquid Sodium chromate add total amount in Sodium chromate content meter for trivalent chromium in raw material with the 0.1-10 of the quality of chromium sesquioxide doubly.
Melting grog after the roasting added cooling in described (c) step, its total amount be in chromite and ferrochrome in the 0.01-2.5 of total chromium sesquioxide quality doubly.
The roasting time of compound in flame kiln is 0.01-0.099h.
In compound, chromite and ferrochrome granularity are all at 0.2-0.01 micron.
The device of Sodium chromate prepared by described mixing chromite and ferrochrome, it is characterized in that: the transmission rig rotated by flame kiln and drive flame kiln forms, being provided with middle part partition wall in the kiln of described flame kiln, continuing oxidation zone by being divided into raw material melt oxidation district and grog melting in kiln;
Kiln body two ends are that two end d1 and d2, end d1 are provided with high-order liquid-phase outlet e, and this high-order liquid-phase outlet e is positioned at the middle and lower part of end d1; A side angle of another end d2 is provided with low level liquid-phase outlet e1, and described e1 is arranged so that can to discharge flame kiln when low level liquid-phase outlet e1 is positioned at flame kiln bottom all or substantially discharge the whole liquid phase grog of kiln completely when flame kiln goes to;
Be provided with one or more BOTTOM OXYGEN rifle bottom flame kiln body, top is provided with one or more tipburn oxygen-blowing gun and charging opening a and exhanst gas outlet c, charging opening a and exhanst gas outlet c are located at two ends, kiln top respectively.
Described transmission rig comprises motor l, step-down gear j, gear driving member i, bearing support m and kiln body basis k, flame kiln is supported on the k of kiln body basis by bearing and bearing support m, bearing connects gear driving member i, gear driving member i is connected drive by step-down gear with motor.
Be provided with 4 BOTTOM OXYGEN rifle f1 bottom described kiln body, f2, f3 and f4, top is provided with 2 tipburn oxygen-blowing gun b1, b2 or 3 tipburn oxygen-blowing gun b1, b2 and b3; Charging opening a is between flame kiln end d2 and tipburn oxygen-blowing gun b1, and exhanst gas outlet c is located at the end d1 of kiln and burns between oxygen-blowing gun b2 or b3.
Described flame kiln is horizontal shape of a hoof flame kiln.
In described kiln, middle part partition wall is provided with low level fused salt siphon port, 0.02-0.5m bottom this siphon port overhead height distance kiln thorax, 0.001-0.48m bottom siphon port bottom level distance kiln thorax.
An explosive door A is provided with, a fire detecting flame temperature device B at the top of kiln.
Described tipburn oxygen rifle adjacent oxygen rifle level interval is 0.1-0.49m; BOTTOM OXYGEN rifle adjacent oxygen rifle level interval is 0.1-0.49m.
Described tipburn oxygen-blowing gun b1, the angle that the setting of b2, b3 should make tipburn oxygen-blowing gun insert the direction of kiln body d and the gravitational vertical line direction of kiln body d is 0-14.5 °; BOTTOM OXYGEN rifle f1, it is 0 ° that f2, f3, f4 arrange the angle that BOTTOM OXYGEN rifle should be made to insert the direction of kiln body d and the gravitational vertical line direction of kiln body d.
Described BOTTOM OXYGEN rifle is single hole plug type oxygen rifle, comprises non-metallic layer skin, oxygen enters pipe p and metal reinforced protective layer R; The outer field internal layer N of non-metallic layer that described oxygen enters pipe p is provided with side pipe o1, the side pipe o2 and one deck annular slot that inert gas flows into; Described non-metallic layer skin is made up of protective sleeve n1, n2, n3, n4, n5 and n6; The middle and lower part of described single hole plug type oxygen rifle is provided with the metal reinforced protective layer R of high temperature resistant anti-oxidation.
Described BOTTOM OXYGEN rifle is porous plug formula oxygen rifle, and comprise non-metallic layer outer r, inlet pipe s and porous escape pipe q, gas is entered in porous escape pipe q by inlet pipe s and enters in kiln.
BOTTOM OXYGEN rifle sprays into the oxygen-rich air or 90-99.99% oxygen that gas is air or 30-50%.
Described tipburn oxygen-blowing gun comprises oxygen inlet pipe x, x1, Sweet natural gas inlet pipe u, non-metallic casing v and three layer of cover gun barrel w; Described oxygen inlet pipe x outside is provided with three layers of cover gun barrel w, and three layers of cover gun barrel w outer setting non-metallic casing v, the sidepiece of oxygen inlet pipe x is provided with gas inlet pipe x1 and Sweet natural gas inlet pipe u.
Tipburn oxygen-blowing gun sprays into the oxygen that gas is 90-99.99%; Described oxygen and Sweet natural gas Thorough combustion, when superfluous oxygen is heated to 1510-1900 DEG C, inner with the fused salt that supersonic speed is injected in roasting.
The composition of the non-metallic material of the non-metallic layer skin of BOTTOM OXYGEN rifle and the refractory brick of flame kiln is Cr according to weight ratio
2o
31-15%, Al
2o
370-90%, SiO
20.5-5%, P
2o
50.1-8%, ZrO
20.5-10%.
The material of the non-metallic casing v of tipburn oxygen-blowing gun is Al
2o
3and/or Si
3n
4; Wherein Al
2o
3and Si
3n
4during mixing, both ratios are 1: 0.01-0.5.
Described material is at 130-140N/mm
2pressure makes type, and 1900-2200 DEG C, 0.5-5h fires and forms.
Present inventor has carried out research extensively and profoundly in the calcium-free roasting field of chromite, find the chromite roasting method that not only there is high productivity but also effectively can solve melting furnace material viscosity higher, be there is by design the reactor of ad hoc structure, make chromite in specific fused-salt medium, carry out liquid phase roasting by ferrochrome and can realize aforementioned object.
In this roasting method, chromite by means of ferrochrome, serves and promotes oxidation of chromite reactivity.For medium carbon ferrochrome, but invention in be not limited to medium carbon ferrochrome, medium carbon ferrochrome main component is Cr65%, Fe31%, C2%, Si1.0%, P≤0.03%, S≤0.1%, other as Ca, Mg, Al be micro substance.Chromite composition is with Cr
2o
350%, Fe
2o
325%, Al
2o
312%, MgO15%, SiO
26% is example, is also not limited only to this type of in invention, and wherein ferrochrome ratio, chromium aluminum ratio, chromium magnesium ratio, chrome-silicon ratio are respectively 1.95,5.93,3.8,12.2; Because in ferrochrome, the ratio of iron, these impurity of silicon and chromium is respectively 2.01 and 65, other impurity ratios are all more than 650.Chromite compares with ferrochrome, deironing this comparatively close to outward, other impurity and ferrochrome ratio are tens times of chromite to hundred times, adding ferrochrome like this makes solid phase impurity in reactor fused salt greatly reduce, reduce fused salt viscosity, fused salt can be made fully to stir, make gas-liquid-solid three-phase form homogeneous phase, make chromite and ferrochrome in fused salt, effectively can carry out oxidizing reaction.Further, due in ferrochrome containing simple substance carbon element, he can rapidly with oxygen Thorough combustion, locally Quick confession fused salt heat, avoid because oxygen temperature is too low and cause needing temperature raising degree in stove to carry out chromic oxide iron ore, such speed of response can be accelerated.By this characteristic of ferrochrome, can avoid the problem that furnace charge is clamminess, and can realize continuous seepage, thus greatly boost productivity, output is identical kiln sectional area without more than 20 times of calcium rotary kiln.Because the reaction times shortens greatly, and greatly can reduce the size of reactor thus, thus reduce facility investment.
Adopted by the method in addition and replace solid Sodium chromate or high chromium concentration acid sodium solution through air-cooled cooling melting grog, can return and produce with raw material granulation, enter kiln together with raw material, to improve the proportional quantity of Sodium chromate in raw material, keep fused salt viscosity not raise because of the enrichment of solid phase impurity; And owing to no longer preparing solid Sodium chromate or high chromium concentration acid sodium solution, can flow process be shortened.The molten materials that flame kiln is discharged is through the cooling of revolving cup high-pressure blast, and the heat energy of hot blast is recyclable carries out cogeneration.Through heat calculation, compared with calcium-free roasting method, can effectively sinking less energy-consumption more than 30%.
This inventive method one advantageously, adds the effect of SODIUMNITRATE.Due at chromite without calcium method and have in calcium method, chromite reaction in early stage forms chromous acid sodium (Na
2oCr
2o
3), then react more than 30 minutes under 1150 DEG C of high temperature, then form Sodium chromate.Add Sodium chromate and in 1 minutes, chromous acid sodium is rapidly converted into Sodium chromate exactly, owing to releasing nitrogen, play stirring action, can prevent dead angle in stove from having solid-phase material to deposit.Principal reaction principle is as follows:
FeO·Cr
2O
3+Na
2CO
3→Na
2O·Cr
2O
3+FeO+CO
2(2)
4Na
2O·Cr
2O
3+3O
2→4Na
2CrO
4+2Cr
2O
3(3)
Cr
2O
3+Na
2CO
3→Na
2O·Cr
2O
3+CO
2(4)
6NaNO
3+7Na
2O·Cr
2O
3→10Na
2CrO
4+2Cr
2O
3+3N
2(5)
The effect of another sodium peroxide advantageously added of this inventive method.Add sodium peroxide and mainly react early stage, the spinel structure of the chromite that accelerates the failure, makes chromite become a micron small-particle from the particle of a 0.074mm, is convenient to chromite and oxygen react, and works in coordination with SODIUMNITRATE, the oxidizing reaction of participation chromous acid sodium.
This inventive method is oxidized from highly beneficial chromite kiln type structure and ferrochrome, and safe and reliable.One is adopt barricade will to be divided into Liang Ge district in kiln, and a district is raw material melt oxidation district, and one is that grog melting continues oxidation zone, avoiding raw material because of short circuit reason, not being discharged by being oxidized in time; Another is the international up-to-date iron and steel of multiple oxygen blast and glass new technology at the bottom of integrated tipburn oxygen blast, makes gas-liquid-solid three-phase fully form homogeneous phase, without dead angle, without deposition, and avoids cold oxygen directly to enter fused salt inside, cause oxidization time to extend, oxidation ratio is reduced; Also have one to be adopt shape of a hoof flame kiln, arrange urgent discharge gate at one jiao of the end face top of kiln like this, this is just different from cylindrical rotary kiln completely, this spline structure is convenient to discharge molten materials completely, be convenient to emergency service, when there is Accident Symptom, play protection personal security and device security; Another is provided with explosion-proof equipment and flame temperature measuring equipment at the top of kiln, solves the hidden danger that natural gas, because burn incompletely is blasted, and is easy to production safety operation.
The nonmetal oxygen rifle material that this inventive method is selected and refractory materials, adapt under 1510-1900 DEG C of high temperature, at carbonate content 20%, Sodium chromate is in the fused-salt medium of 80%, pass into pure oxygen, the end rifle life-span reaches more than 1 year, and rifle of the general end only has the life-span of 30 days; The tipburn oxygen-blowing gun life-span reaches more than 5 years, and the general top blast rifle life-span only has 6 months; Refractory brick life can reach 5 year life-span, and general bottom convertor refractory brick longer life-span is 4 years.Because tipburn oxygen-blowing gun non-metallic material here select the material such as silicon nitride, aluminium sesquioxide to make, BOTTOM OXYGEN rifle and refractory brick add some natural crystals, mixing material contains the compositions such as chromium sesquioxide, aluminium sesquioxide, silicon-dioxide, zirconium dioxide, Vanadium Pentoxide in FLAKES, and cold crushing strength (CCS) reaches 140N/mm
2, proportion reaches 3.33g/cm
3.
This inventive method oxidation ratio and grog leaching rate high, oxidation ratio reaches more than 98%, and leaching rate reaches 99.97%, chromium yield 97.96%.And the by product obtained is high scum, and sexavalent chrome is low is only 0.1%, is less than 20% without calcium.Adopt this method, one ton of sodium dichromate can output height scum 300 kilograms, and it is few to produce the quantity of slag, and being have calcium less than 20%, is less than 40% without calcium, is less than 70% of pure chromite fusion smelting method.Can be directly used in smelting ferrochrome, the ferrochrome after smelting returns roasting, realizes recycling economy, and reduces production cost more than 20%.
The present invention uses for reference domestic and international smelting iron and steel, nonferrous metallurgy, glass furnace technology, adopt special flame kiln, chromite is made to be oxidized in melting liquid phase in molten salt system by ferrochrome, greatly increase the transformation efficiency of chromium, add output, fundamentally solve the problem that calcium-free roasting technique easily ties wall, and solve the problem for the treatment of of chromate slag difficulty.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the inventive method flame kiln used.
Fig. 2-1 is the schematic diagram of the single tube BOTTOM OXYGEN rifle of the inventive method flame kiln used
Fig. 2-2 is cross-sectional views of the single tube BOTTOM OXYGEN rifle of the inventive method flame kiln used
Fig. 2-3 is schematic diagram of the multitube BOTTOM OXYGEN rifle of the inventive method flame kiln used
Fig. 2-4 is cross-sectional views of the multitube BOTTOM OXYGEN rifle of the inventive method flame kiln used
Fig. 3 is the schematic diagram of the tipburn oxygen-blowing gun of the inventive method flame kiln used
Fig. 4 is the inventive method process flow sheet
In figure, 1-charging opening a, 201-top blast burns oxygen-blowing gun b1, 202-top blast burns oxygen-blowing gun b2, 203-top blast burns oxygen-blowing gun b3, 3-exhanst gas outlet c, 4-horizontal flame kiln kiln body d, 401-kiln end face d1, 402-kiln end face d2, 501-high-order melting liquid-phase outlet e, 502-melting liquid phase emergency service outlet e1, 7-low level liquid phase siphon port g, 8-kiln internal partition wall h, 601-BOTTOM OXYGEN rifle f1, 602-BOTTOM OXYGEN rifle f2, 603-BOTTOM OXYGEN rifle f3, 604-BOTTOM OXYGEN rifle f4, 9-wheel gearing i, 10-step-down gear j, 11-kiln body basis k, 12-electric machine l, 13-bearing support m, the outer field internal layer N of 14-non-metallic layer, 1401-protective sleeve n1, 1402-protective sleeve n2, 1403-protective sleeve n3, 1404-protective sleeve n4, , 1405-protective sleeve n5, 1406-protective sleeve n6, 1501-side pipe o1, 1502-side pipe o2, 16-oxygen enters pipe p, 17-porous escape pipe q, the outer r of 18-non-metallic layer, 19-inlet pipe s, 21-Sweet natural gas inlet pipe u, 22-non-metallic casing v, 23-tri-layers overlaps gun barrel w, 2401-oxygen inlet pipe x, 2402-oxygen inlet pipe x1, the metal reinforced protective layer R of 27-
Embodiment
According to the method for the melting liquid phase multifuel combustion oxidation of chromite of the present invention and ferrochrome, comprise and first chromite and ferrochrome are machined to 0.2-0.01 micron, then chromite will be comprised, ferrochrome, soda ash, SODIUMNITRATE, sodium peroxide, through metering mixing, in granulating disc, rear liquid Sodium chromate carries out granulation with leaching, the hot gas that the raw material forming particle are come by flame kiln in three rotary drum drying machines carries out drying, dried particle raw material enter in chromite and ferrochrome flame kiln together with melting grog after cooling, in the presence of oxygen in 1510-1900 DEG C, roasting at preferred 1550-1650 DEG C, chromite and ferrochrome is made to carry out decomposition oxidation in melting liquid phase in fused-salt medium, obtain sodium chromate chamotte.After clinker cooling, then use hot water subsequent leaching in subsequent leaching groove, leaching slip goes band filter to carry out continuous filtration washing, and obtain chromaking work primary products liquid Sodium chromate, the slag of eliminating is high scum, goes to smelt ferrochrome, returns preparation of raw material.The flue gas that flame kiln is discharged and cooling molten materials, by the air heated, are used and are carried out exhaust heat recovery power generation.Wherein said flame kiln is horizontal shape of a hoof flame kiln, this flame kiln comprises kiln body and is positioned at two ends at these kiln body two ends, middle and lower part, an end is provided with the normal liquid-phase outlet produced, another end top side angle is provided with maintenance melting liquid phase relief outlet, one or more oxygen rifle and one or more charging opening is provided with at kiln body top, and exhanst gas outlet is set above kiln portion, preferred described kiln body is the shape of a hoof.One or more oxygen rifle is provided with in the bottom of kiln.In kiln, middle part, is provided with partition wall and low level fused salt siphon port, 0.02-0.5m bottom siphon port overhead height distance kiln thorax, 0.001-0.48m bottom siphon port bottom level distance kiln thorax.And be provided with explosive door and temperature measuring equipment at the top of kiln.Tipburn oxygen blows rifle and BOTTOM OXYGEN rifle spacing is 0.2-0.49 rice.
In the methods of the invention, feed the compound carrying out oxidizing roasting in chromite and ferrochrome flame kiln and comprise chromite and ferrochrome; Be suitable for the chromite of the inventive method and ferrochrome normally in chromite chromium content count 35 % by weight and those above chromites with chromium sesquioxide, in ferrochrome, chromium content counts 73 % by weight and those above ferrochrome with chromium sesquioxide.Except chromite and ferrochrome, treat that the compound of roasting also comprises the compound of soda ash, SODIUMNITRATE, sodium peroxide, liquid Sodium chromate, cooled melting grog.Advantageously, treat that the compound of roasting comprises the compound of Sodium chromate, ferrochrome, cooled melting grog, through roasting oxidation, the viscosity of molten materials can be reduced; Compound also comprises SODIUMNITRATE and sodium peroxide, and object is the oxidizing reaction accelerating chromite and ferrochrome, Reaction time shorten;
In described compound, ferrochrome add total amount be the 0.01-100 of chromite quality doubly;
The total amount that adds of soda ash is that in raw material trivalent chromium is in the 1.2-3 of the quality of chromium sesquioxide doubly;
The total amount that adds of SODIUMNITRATE is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly;
In described compound, the total amount that adds of sodium peroxide is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly.
In described chromite, chromium content counts >=35wt% with chromium sesquioxide, and in ferrochrome, chromium content counts >=73wt% with chromium sesquioxide.
Wherein in compound during balling-up, in the liquid Sodium chromate added, Sodium chromate concentration is 200-500 grams per liter, its liquid Sodium chromate add total amount in Sodium chromate content meter for trivalent chromium in raw material with the 0.1-10 of the quality of chromium sesquioxide doubly.
Should be understood that, treat that the compound of roasting advantageously should Granular forms feed in flame kiln.Treating that the compound of roasting feeds in flame kiln with spherule shape form (such as pelletizer or piston press granulation) can avoid dust to the pollution of environment.Usual employing be pelletizer.
The roasting of compound in flame kiln, usually at 1510-1900 DEG C, is carried out at preferred 1550-1650 DEG C.The selection of temperature is relevant to the fusing point of other material except chromite and ferrochrome.The selection of maturing temperature must guarantee that chromite carries out oxidizing reaction in liquid phase flow fused salt, that is, smelt known liquid phase oxidation in production Sodium chromate field with chromite and carry out.Roasting time in flame kiln is generally 0.001-0.099h.
By the inventive method by compound roasting in the presence of oxygen, produce grog, this grog contains a large amount of water-soluble Sodium chromate.Aftertreatment is carried out to this grog and can obtain chromium acid sodium alkaline liquid, and obtain by-product height scum simultaneously.This is undertaken by usual manner, such as, by grog leaching.Generally select band filter, to realize filtration washing serialization.Described high scum can reach more than 50 % by weight in ferric oxide content, can be directly used in smelting ferrochrome, and the ferrochrome of production can roasting again in Returning reactor.
In order to realize the Continuous Liquid Phase melting roasting of the inventive method, employ a kind of specialized designs for this destination device, this device is a horizontal shape of a hoof flame kiln, this flame kiln comprises kiln body and is positioned at two ends at these kiln body two ends, middle and lower part, an end is provided with high-order liquid-phase outlet, another end upper side angle is provided with maintenance liquid-phase outlet, and the middle part of kiln is provided with partition wall, is provided with status siphon port in partition wall.Be provided with one or more oxygen rifle on bottom kiln body, be provided with one or more burning oxygen blast at kiln top and burn rifle and one or more charging opening.Preferably, the kiln body of flame kiln is the shape of a hoof.
In roasting process, kiln body both can turn round and also can not turn round, and for economic reasons, did not usually advantageously turn round.When needs overhaul, need kiln body to turn round.
In a preferred embodiment of the inventive method, horizontal flame kiln used as shown in Figure 1.This flame kiln comprises horse shoe flame furnace body d and is positioned at two end d1 and d2 at these kiln body two ends.An end d1 is provided with high-order liquid-phase outlet e, and the liquid phase grog that roasting obtains enters refrigerating work procedure by high-order liquid-phase outlet e, then to leaching operation, this high-order liquid-phase outlet e is usually located at the middle and lower part of end d1.D2 side angle in another end is provided with low level liquid-phase outlet e1, its setting should make can to discharge kiln all liquid phase grogs or substantially discharge the whole liquid phase grog of kiln completely when low level liquid-phase outlet e1 is positioned at rotary kiln bottom when rotary kiln goes to, this low level liquid-phase outlet uses when whole liquid phase grog discharged by needs from kiln, such as, when overhauling.Therefore, the position of high-order liquid-phase outlet e usually compared with low level liquid-phase outlet e1 closer to melting liquid phase level during roasting.Be provided with 4 BOTTOM OXYGEN rifle f1 with it at kiln, f2, f3, f4 are to feed the oxygen-containing gas of oxygen needed for roasting as air.Advantageously, burn oxygen-blowing gun b1, b2, b3 are positioned at the top of horizontal flame kiln d, and kiln body top is also provided with 1 charging opening a, to feed the compound treating roasting.And be provided with an explosive door A at the top of kiln, a fire detecting flame temperature device B.Advantageously, charging opening a, between horizontal revolving kiln end d2 and tipburn oxygen-blowing gun b1, the kiln body top between the end d1 and burning oxygen-blowing gun b3 of kiln is also provided with exhanst gas outlet c, to shift out the gas that roasting produces.
Burn oxygen-blowing gun b1, b2, b3 by the pressure of inflammable gas and flow control flame kiln temperature, and by pure oxygen with hypersonic velocity when being heated, be blown in melt.It should be noted that the structure of the flow velocity of oxygen, flow, pressure and rifle, should ensure that oxygen fully stirs and participates in oxidizing reaction, and in order to only reach this object, oxygen hypervelocity superpressure, and make oxygen directly reach refractory brick top, thus easily burn refractory brick.Flame kiln d also comprises transmission mechanism, for the revolution realizing flame kiln d; This transmission mechanism generally includes motor l step-down gear j gear i.As flame kiln, this device also comprise bearing support m and kiln body basis k, its bottom bracket m effect be to flame kiln d rise support and booster flame kiln d turn round.In a particularly preferred embodiment of the inventive method, as shown in Figure 2, this figure is that this oxygen rifle divides single tube and multitube two kinds of forms to the BOTTOM OXYGEN rifle of flame kiln used, provides the oxygen-containing gas of oxygen needed for roasting.Single tube and multitube oxygen rifle are plug type, easy access.In single tube oxygen rifle; oxygen is entered by p pipe; in the nitrogen inert gas that the outer tube of shower nozzle gas channel is flow through at a high speed by o1, o2 pipe; one deck annular slot is provided with at rifle head; can not only cooling spray be strengthened, and avoid oxygen rifle and directly contact with fused salt, thus shower nozzle is shielded; delay deterioration, extend work-ing life.Which ensure that air-flow sprays with the form of mushroom head, and prevent oxygen rifle dross.And outside metal barrel, being arranged with nonmetal protective sleeve n1, n2, n3, n4, n5, n6, anti-block rifle is too fast oxidized.Single tube BOTTOM OXYGEN rifle middle and lower part is provided with the metal reinforced protective layer of high temperature resistant anti-oxidation.In multitube oxygen rifle, entered in air inflow q gun barrel by s pipe and enter in kiln, and nonmetal protective sleeve r is set, extend life-span of oxygen lance.
In another particularly preferred embodiment of the inventive method, the tipburn oxygen-blowing gun of flame kiln used as shown in Figure 3.This tipburn oxygen-blowing gun oxygenous inlet pipe x, x1, Sweet natural gas inlet pipe u, non-metallic casing v and three layer of cover gun barrel w.Advantageously, oxygen is excessive, Sweet natural gas Thorough combustion; when superfluous oxygen is heated to 1510-1900 DEG C, injects fused salt inside with supersonic speed, make chromite and ferrochrome fully oxidized; and owing to burning oxygen-blowing gun under nonmetal protective sleeve protection, the life-span greatly extends.
As the oxygen-containing gas fed from oxygen rifle, bottom blown gas, is preferably air.Tipburn is blown for 90-99.99% pure oxygen gas, and the infeed of this oxygen rich gas not only can strengthen roasting process, improves productivity, and can reduce burnup, decreases smoke discharge amount.
In the present invention, tipburn oxygen-blowing gun b1, b2, b3 and BOTTOM OXYGEN rifle f1, f2, f3, f4 level interval is 0.1-0.49m.Described tipburn oxygen-blowing gun b1, the angle that the setting of b2, b3 should make tipburn oxygen-blowing gun insert the direction of kiln body d and the gravitational vertical line direction of kiln body d is 0-14.5 °; BOTTOM OXYGEN rifle f1, it is 0 ° that f2, f3, f4 arrange the angle that BOTTOM OXYGEN rifle should be made to insert the direction of kiln body d and the gravitational vertical line direction of kiln body d.
The inventive method improves the transformation efficiency of chromite and ferrochrome, reduces production cost, has saved the energy, has effectively improve throughput, and makes the high scum of generation again produce ferrochrome, returns recycle.This is the great innovation of chromic salts cleanly production.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
In following embodiment, the chromite of use is India's chromite, and its content counts 50wt% with chromium sesquioxide, and use ferrochrome to be domestic product medium carbon ferrochrome, its content counts 95wt% with chromium sesquioxide.The soda ash used, carbonate content is 98wt%.The liquid Sodium chromate used, in Sodium chromate 300 grams per liter.The SODIUMNITRATE content used is 98wt%.The sodium peroxide content used is 98wt%.After the melting cooling used, grog is containing Sodium chromate 85wt%.
The roasting apparatus used in embodiment 1-3 is flame kiln as shown in Figure 1, wherein: this flame kiln is the horse shoe flame furnace of the wide 3.0m of long 4.0m height 3.0m, there are 4 along the axial oxygen rifle f1 on the same line of flame kiln clump with it at kiln, f2, f3, f4, is also provided with charging opening c with it at kiln by each two on the partition wall both sides of kiln; Flame kiln top, is provided with and burns oxygen-blowing gun 2, b1, b2.Tipburn oxygen-blowing gun and each adjacent flat spacing 0.4m of oxygen rifle of BOTTOM OXYGEN rifle; Its longitudinal direction of tipburn oxygen-blowing gun b1, b2 is 14 ° with the angle in the gravitational vertical line direction of kiln body d.BOTTOM OXYGEN rifle f1, f2, f3, f4 are arranged so that its longitudinal direction is 0 ° with the angle in the gravitational vertical line direction of kiln body d.
Charging opening a is between horizontal revolving kiln end d2 and tipburn oxygen-blowing gun b1, and exhanst gas outlet c is between the end d1 and burning oxygen-blowing gun b2 or b3 of kiln.
BOTTOM OXYGEN rifle has structure shown in Fig. 2, is this oxygen rifle multitube form of this figure, provides the oxygen-containing gas of oxygen needed for roasting.Multitube oxygen rifle is plug type, easy access.During production, entered in air inflow q gun barrel by s pipe and enter in kiln, and nonmetal protective sleeve r is set, extend life-span of oxygen lance.Tipburn oxygen-blowing gun as shown in Figure 3.This tipburn oxygen-blowing gun oxygenous inlet pipe x, x1, Sweet natural gas inlet pipe u, non-metallic casing v and gun barrel w.
Embodiment 1
1. be chromite (in chromium sesquioxide) according to mass ratio: ferrochrome (in chromium sesquioxide): soda ash: SODIUMNITRATE: sodium peroxide: liquid Sodium chromate: grog=1 after melting cooling: 0.5: 2.0: 0.02: 0.02: 4.5: 0.5, coordinate balling-up, obtain granular raw material;
2. by charging opening a, granular raw material are added in the horizontal flame kiln of the shape of a hoof, start top blast and burn oxygen rifle b1, b2, temperature of reaction is controlled to be 1550 DEG C, and keeps 60min at this temperature;
3. then, by BOTTOM OXYGEN rifle f1, f2, f3, f4 constantly spray into air in horizontal flame kiln, and at 1550 DEG C of reaction 5min, reaction mixture is melting liquid phase in the process;
4. the gas produced in horizontal flame kiln shifts out from exhanst gas outlet, liquid phase grog shifts out through high-order liquid-phase outlet, make in revolving cup at an alloy material, cool with high pressure cold stream, after cooling, in the leaching groove of band blade, hanker water with 90 DEG C carry out subsequent leaching, and continuous filtration washing in band filter, obtain chromium acid sodium alkaline liquid and scum.Chrome ore transformation efficiency (chromium in chromite changes into the per-cent of the soluble chromium in chromium acid sodium alkaline liquid) is 92.50% after measured, scum in the iron level of ferric oxide for 58.20wt%.
Embodiment 2
1. be chromite (in chromium sesquioxide) according to mass ratio: ferrochrome (in chromium sesquioxide): soda ash: SODIUMNITRATE: sodium peroxide: liquid Sodium chromate: grog=1 after melting cooling: 10: 18.50: 0.15: 0.15: 22: 7.0, coordinate balling-up, obtain granular raw material;
2. by charging opening a, granular raw material are added in the horizontal flame kiln of the shape of a hoof, start top blast and burn oxygen rifle b1, b2, temperature of reaction is controlled to be 1650 DEG C, and keeps 40min at this temperature;
3. then, by BOTTOM OXYGEN rifle f1, f2, f3, f4 constantly spray into air in horizontal flame kiln, and at 1650 DEG C of reaction 3min, reaction mixture is melting liquid phase in the process;
4. the gas produced in horizontal flame kiln shifts out from exhanst gas outlet, liquid phase grog shifts out through high-order liquid-phase outlet, make in revolving cup at an alloy material, cool with high pressure cold stream, after cooling, in the leaching groove of band blade, hanker water with 90 DEG C carry out subsequent leaching, and continuous filtration washing in band filter, obtain chromium acid sodium alkaline liquid and scum.Chrome ore transformation efficiency (that is, the chromium in chromite changes into the per-cent of the soluble chromium in chromium acid sodium alkaline liquid, lower with) is 95.25% after measured, scum in the iron level of ferric oxide for 61.32wt%.
Embodiment 3
1. be chromite (in chromium sesquioxide) according to mass ratio: ferrochrome (in chromium sesquioxide): soda ash: SODIUMNITRATE: sodium peroxide: liquid Sodium chromate: grog=1 after melting cooling: 50: 100: 1: 1: 100: 35, coordinate balling-up, obtain granular raw material;
2. by charging opening a, granular raw material are added in the horizontal flame kiln of the shape of a hoof, start top blast and burn oxygen rifle b1, b2, temperature of reaction is controlled to be 1850 DEG C, and keeps 40min at this temperature;
3. then, by BOTTOM OXYGEN rifle f1, f2, f3, f4 constantly spray into air in horizontal flame kiln, and at 1850 DEG C of reaction 2min, reaction mixture is melting liquid phase in the process;
4. the gas produced in horizontal flame kiln shifts out from exhanst gas outlet, liquid phase grog shifts out through high-order liquid-phase outlet, make in revolving cup at an alloy material, cool with high pressure cold stream, after cooling, in the leaching groove of band blade, hanker water with 90 DEG C carry out subsequent leaching, and continuous filtration washing in band filter, obtain chromium acid sodium alkaline liquid and scum.Chrome ore transformation efficiency (that is, the chromium in chromite changes into the per-cent of the soluble chromium in chromium acid sodium alkaline liquid, lower with) is 98.73% after measured, scum in the iron level of ferric oxide for 62.51wt%.
Claims (17)
1. a method for Sodium chromate prepared by mixing chromite and ferrochrome, it is characterized in that, is made up of following steps:
A () chromite and ferrochrome, mix after metering with soda ash, SODIUMNITRATE, sodium peroxide, by this compound, in granulating disc, rear liquid Sodium chromate carries out granulation with leaching;
The hot gas that b raw material that () forms particle are come by flame kiln in three rotary drum drying machines carries out drying;
C () dried particle raw material enter flame kiln together with melting grog after cooling, under oxygen or air exist, adopt mixing chromite and the ferrochrome of making of multiple oxygen blast at the bottom of tipburn oxygen blast to carry out decomposition oxidation in melting liquid phase in fused-salt medium, obtain sodium chromate chamotte;
D () grog, after the cooling of revolving cup high-pressure blast, uses hot water subsequent leaching in subsequent leaching groove;
E (), to the continuous filtration washing in filter of leaching slip, obtains chromaking work primary products liquid Sodium chromate;
In described compound, ferrochrome add total amount be the 0.01-100 of chromite quality doubly;
The total amount that adds of soda ash is that in raw material trivalent chromium is in the 1.2-3 of the quality of chromium sesquioxide doubly;
The total amount that adds of SODIUMNITRATE is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly;
In described compound, the total amount that adds of sodium peroxide is that in raw material trivalent chromium is in the 0.01-0.5 of the quality of chromium sesquioxide doubly;
Wherein in compound during balling-up, in the liquid Sodium chromate added, Sodium chromate concentration is 200-500 grams per liter, its liquid Sodium chromate add total amount in Sodium chromate content meter for trivalent chromium in raw material with the 0.1-10 of the quality of chromium sesquioxide doubly;
Melting grog after the roasting added cooling in described (c) step, its total amount be in chromite and ferrochrome in the 0.01-2.5 of total chromium sesquioxide quality doubly;
Maturing temperature in described (c) step is 1510-1900 DEG C;
The roasting time of described compound in flame kiln is 0.01-0.099h.
2. the method for Sodium chromate prepared by mixing chromite as claimed in claim 1 and ferrochrome, it is characterized in that: the flue gas that described flame kiln is discharged and revolving cup high-pressure blast cool grog and by the air heated, enter waste heat recovery generating system.
3. the method for Sodium chromate prepared by mixing chromite as claimed in claim 1 and ferrochrome, it is characterized in that: the high scum that described (e) step is discharged enters smelts ferrochrome system.
4. the method for Sodium chromate prepared by mixing chromite as claimed in claim 1 and ferrochrome, it is characterized in that: the maturing temperature in described (c) step is 1550-1650 DEG C.
5. the method for Sodium chromate prepared by mixing chromite as claimed in claim 1 and ferrochrome, it is characterized in that: in described chromite, chromium content counts >=35wt% with chromium sesquioxide, and in ferrochrome, chromium content counts >=73wt% with chromium sesquioxide.
6. the method for Sodium chromate prepared by mixing chromite as claimed in claim 1 and ferrochrome, it is characterized in that: in compound, chromite and ferrochrome granularity are all at 0.01-0.2 micron.
7. the device of Sodium chromate prepared by a mixing chromite as described in one of claim 1-6 and ferrochrome, it is characterized in that: the transmission rig rotated by flame kiln and drive flame kiln forms, being provided with middle part partition wall in the kiln of described flame kiln, continuing oxidation zone by being divided into raw material melt oxidation district and grog melting in kiln;
Kiln body two ends are that two end d1 and d2, end d1 are provided with high-order liquid-phase outlet e, and this high-order liquid-phase outlet e is positioned at the middle and lower part of end d1; A side angle of another end d2 is provided with low level liquid-phase outlet e1, and described e1 is arranged so that can to discharge flame kiln when low level liquid-phase outlet e1 is positioned at flame kiln bottom all or substantially discharge the whole liquid phase grog of kiln completely when flame kiln goes to;
Be provided with one or more BOTTOM OXYGEN rifle bottom flame kiln body, top is provided with one or more tipburn oxygen-blowing gun and charging opening a and exhanst gas outlet c, charging opening a and exhanst gas outlet c are located at two ends, kiln top respectively;
Described tipburn oxygen-blowing gun comprises oxygen inlet pipe x, x1, Sweet natural gas inlet pipe u, non-metallic casing v and three layer of cover gun barrel w; Described oxygen inlet pipe x outside is provided with three layers of cover gun barrel w, three layers of cover gun barrel w outer setting non-metallic casing v, and the sidepiece of oxygen inlet pipe x is provided with gas inlet pipe x1 and Sweet natural gas inlet pipe u;
Described tipburn oxygen-blowing gun sprays into the oxygen that gas is 90-99.99%; Described oxygen and Sweet natural gas Thorough combustion, when superfluous oxygen is heated to 1510-1900 DEG C, inner with the fused salt that supersonic speed is injected in roasting;
The material of the non-metallic casing v of described tipburn oxygen-blowing gun is Al
2o
3and/or Si
3n
4; Wherein Al
2o
3and Si
3n
4during mixing, both ratios are 1:0.01-0.5; Described material is at 130-140N/mm
2pressure makes type, and 1900-2200 DEG C, 0.5-5h fires and forms;
Described flame kiln is horizontal shape of a hoof flame kiln.
8. the device of Sodium chromate prepared by mixing chromite as claimed in claim 7 and ferrochrome, it is characterized in that: described transmission rig comprises motor l, step-down gear j, gear driving member i, bearing support m and kiln body basis k, flame kiln is supported on the k of kiln body basis by bearing and bearing support m, bearing connects gear driving member i, gear driving member i is connected drive by step-down gear with motor.
9. the device of Sodium chromate prepared by mixing chromite as claimed in claim 7 and ferrochrome, it is characterized in that: be provided with 4 BOTTOM OXYGEN rifle f1 bottom described kiln body, f2, f3 and f4, and top is provided with 2 tipburn oxygen-blowing gun b1, b2 or 3 tipburn oxygen-blowing gun b1, b2 and b3; Charging opening a is between flame kiln end d2 and tipburn oxygen-blowing gun b1, and exhanst gas outlet c is located between the end d1 of kiln and tipburn oxygen-blowing gun b2 or b3.
10. the device of Sodium chromate prepared by mixing chromite as claimed in claim 7 and ferrochrome, it is characterized in that: in described kiln, middle part partition wall is provided with low level fused salt siphon port, 0.02-0.5m bottom this siphon port overhead height distance kiln thorax, 0.001-0.48m bottom siphon port bottom level distance kiln thorax.
The device of Sodium chromate prepared by 11. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: be provided with an explosive door A at the top of kiln, a fire detecting flame temperature device B.
The device of Sodium chromate prepared by 12. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: described tipburn oxygen rifle adjacent oxygen rifle level interval is 0.1-0.49m; BOTTOM OXYGEN rifle adjacent oxygen rifle level interval is 0.1-0.49m.
The device of Sodium chromate prepared by 13. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: described tipburn oxygen-blowing gun b1, the angle that the setting of b2, b3 should make tipburn oxygen-blowing gun insert the direction of kiln body d and the gravitational vertical line direction of kiln body d is 0-14.5 °; BOTTOM OXYGEN rifle f1, it is 0 ° that f2, f3, f4 arrange the angle that BOTTOM OXYGEN rifle should be made to insert the direction of kiln body d and the gravitational vertical line direction of kiln body d.
The device of Sodium chromate prepared by 14. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: described BOTTOM OXYGEN rifle is single hole plug type oxygen rifle, comprises non-metallic layer skin, oxygen enters pipe p and metal reinforced protective layer R; The outer field internal layer N of non-metallic layer that described oxygen enters pipe p is provided with side pipe o1, the side pipe o2 and one deck annular slot that inert gas flows into; Described non-metallic layer skin is made up of protective sleeve n1, n2, n3, n4, n5 and n6; The middle and lower part of described single hole plug type oxygen rifle is provided with the metal reinforced protective layer R of high temperature resistant anti-oxidation.
The device of Sodium chromate prepared by 15. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: described BOTTOM OXYGEN rifle is porous plug formula oxygen rifle, comprise non-metallic layer outer r, inlet pipe s and porous escape pipe q, gas is entered in porous escape pipe q by inlet pipe s and enters in kiln.
The device of Sodium chromate prepared by 16. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: BOTTOM OXYGEN rifle sprays into the oxygen-rich air or 90-99.99% oxygen that gas is air or 30-50%.
The device of Sodium chromate prepared by 17. mixing chromites as claimed in claim 7 and ferrochrome, it is characterized in that: the composition of the non-metallic material of the non-metallic layer skin of BOTTOM OXYGEN rifle and the refractory brick of flame kiln is Cr according to weight ratio
2o
31-15%, Al
2o
370-90%, SiO
20.5-5%, P
2o
50.1-8%, ZrO
20.5-10%.
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| CN103668301B (en) * | 2013-12-11 | 2016-08-24 | 中国科学院青海盐湖研究所 | Electrolysis is utilized to prepare the apparatus and method of chromium acid sodium solution |
| CN104596286B (en) * | 2014-09-01 | 2016-05-11 | 中钢集团耐火材料有限公司 | A kind of bottom convertor isolating and protecting device |
| EP3020690A1 (en) * | 2014-11-13 | 2016-05-18 | LANXESS Deutschland GmbH | Method for reducing hexavalent chromium in oxidic solids |
| CN109402378B (en) * | 2017-08-18 | 2021-01-19 | 湖北振华化学股份有限公司 | Method for extracting chromium from chromium-containing material through oxidizing roasting |
| CN108910950B (en) * | 2018-10-12 | 2020-12-01 | 成都铬科高化工技术有限责任公司 | Method for preparing sodium chromate from chromite |
| CN110042256B (en) * | 2019-04-29 | 2021-04-02 | 中南大学 | Method for recovering chromium from ferronickel smelting slag and preparing light heat-insulating material |
| CN109971970B (en) * | 2019-04-29 | 2021-04-02 | 中南大学 | Method for recovering chromium from ferronickel smelting slag and preparing geopolymer |
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| WO2004083123A1 (en) * | 2003-03-19 | 2004-09-30 | Institute Of Process Engineering Chinese Academy Of Sciences | Method for production of alkali metal chromates |
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| CN1109026A (en) * | 1993-09-30 | 1995-09-27 | 拜尔公司 | Method for manufacturing alkali chromates from chromium ore |
| CN1104258A (en) * | 1993-12-24 | 1995-06-28 | 化学工业部天津化工研究院 | Calcium-less granulating roasting chrominm salt production technology |
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