CN103086432B - Rotary kiln device for sodium dichromate production by calcium-free calcination - Google Patents
Rotary kiln device for sodium dichromate production by calcium-free calcination Download PDFInfo
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- CN103086432B CN103086432B CN201310075579.3A CN201310075579A CN103086432B CN 103086432 B CN103086432 B CN 103086432B CN 201310075579 A CN201310075579 A CN 201310075579A CN 103086432 B CN103086432 B CN 103086432B
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Abstract
The invention discloses a rotary kiln device for sodium dichromate production by calcium-free calcination, and belongs to the technical field of a rotary kiln. The length-diameter ratio of the kiln body is 3-6, wherein the feed end is provided with a feed port, a feed end burner and a smoke outlet, and the discharge end is provided with a siphon high-level outlet, a slag tap and a discharge end burner; a bottom blow-off nozzle device is arranged at the bottom of the kiln body, lateral blow-off nozzle devices are symmetrically arranged at two sides of the kiln body, a top blow-off nozzle device is arranged on the top of the kiln body, and the lengths of the arranged top blow-off nozzle device, the lateral blow-off nozzle devices and the bottom blow-off nozzle device are respectively 30 to 70 percent of the length of the kiln body; the top blow-off nozzle device, the lateral blow-off nozzle devices and the bottom blow-off nozzle device are horizontally arranged and respectively connected with a spray gun; and a power mechanism is arranged on the kiln body, and comprises a transmission device and a gear ring. According to the rotary kiln device, the oxidation reaction time is remarkably shortened, the production capacity is remarkably improved, the production cost is greatly reduced, and the chromite oxidation rate is high, so that an industrial scale can be easily formed.
Description
Technical field
The present invention relates to rotary kiln technical field, more particularly, relate to a kind of rotary kiln device of sodium dichromate production by calcium-free calcination.
Background technology
Sodium dichromate 99 is the main product of Chrome Salt Industry, as basic chemical raw materials, be widely used in the industries such as chemical industry, light industry, printing and dyeing, medicine, the chromic salts series product such as chromic trioxide, chromium hydroxide, basic chromium sulfate can be processed as further, for the industry such as metallurgy, machinery, building materials, oil, process hides, plating, pigment, haberdashery and hardware, in national economy, occupy critical role, sodium dichromate 99 basic production technique is oxidation of chromite roasting-sulfuric acid acidation method.
Traditional sodium dichromate 99 production technique is: chromite has calcium roasting Sodium chromate to form sodium dichromate 99 after sulfuric acid acidation, calcareous (rhombspar, marble or unslaked lime etc.) filler is in a large number used owing to there being calcium roasting, cause bed drain purge large, and have the generation of carcinogens-yellow ultramarine, be difficult to thoroughly removing toxic substances and comprehensive utilization, have a strong impact on environment, be listed in production technique out of category in national industrial policies.
Existing calcium-free roasting production technique does not add calcareous filler, and bed drain purge is few and not containing carcinogens-yellow ultramarine, alleviate environmental influence.Its reaction mechanism is: when chromite is heated to 500 DEG C, Fe
2+first Fe is oxidized to
3+, picotite lattice distorts, and potential energy raises, and is easy to reaction.Soda ash is same R first
2o
3naRO is produced in reaction
2i.e. chromous acid sodium (NaCrO
2), sodium aluminate (NaAlO
2) and sodium ferrite (NaFeO
2), in high temperature oxidative atmosphere, chromous acid sodium continues reaction with oxygen and soda ash and produces Sodium chromate (Na
2crO
4), sodium aluminate and sodium ferrite also play a part alkali, make chromous acid sodium be oxidized to Sodium chromate, due to these three kinds of NaRO
2fusing point all higher than the normal maturing temperature of chrome ore, during normal oxidation roasting, produce the mixture of eutectic melting point in the reaction, cause ring formation in rotary kiln (knurl), be unfavorable for the steady running of producing, at present conventional measure has:
(1) add a large amount of return slag, reduce amount of liquid phase, adopt granulating roasting technique (China Patent Publication No.: CN 1104258A) effectively can reduce ring formation in kiln (knurl), but owing to increasing granulating working procedure, elongated technical process, pellet is dried increases energy consumption.The reaction kinetics research of chromite calcium-free roasting shows: filler than for 0 few alkali roasting, activation energy is 50.3KJ/K.mol; Filler is than the sufficient alkali roasting being 1.5, and activation energy is 73.2KJ/K.mol; The sufficient alkali calcium-free roasting reaction times of the time return slags needed in a basic balance at 1000 DEG C is than many 3 times of few alkali calcium-free roasting (or having calcium roasting).This is also cause the existing major cause low without calcium returning charge foot alkali filler rotary kiln productivity.Granulating roasting technique causes stove productivity to reduce, produces comprehensive cost rising.
(2) by calcium-free roasting reaction mechanism, adopt baking inphases method (Chinese patent grant number: CN 1052461C), the mixture that first stage is made up of the barren rock after chrome ore, alkali metal compound and optional ore dressing contains no more than 2%(volume in one) be heated to temperature between 1000 DEG C to 1400 DEG C in the atmosphere of oxygen, and in subordinate phase, this mixture is oxidized then at least contain the atmosphere situation of the oxygen of 70% at the lesser temps of 900 ~ 1070 DEG C and in supply under, and this method nucleus equipment is two tube kilns and gas segregation scheme.Because technical process is long, equipment especially gas partitions service is complicated, at present still without comparatively successful commercialization example.
(3) chromite pressurized fluid phase oxidation legal system Sodium chromate technique is: add high density concentrated base (NaOH) liquid of 4-6 doubly after solid caustic soda (NaOH) adjusts after chromite and circulation alkali liquor wet-milling, mix, in 4.5 ~ 6.0MPa pressure, under 260 ~ 300 DEG C of temperature condition, carry out pressurization liquid phase oxidation reaction, reaction times 4 ~ 8h, reaction residual liquor is after solid-liquid separation, mother liquor returns batching as circulation alkali liquor, solid part and the solid phase such as crystals of sodium chromate and scum impurity, after dissolving, washing and filtering, solid is scum, liquid adds milk of lime except matter, filtration washing, solid is calcium slag, liquid is through multiple-effect evaporation crystallization, solid is for containing alkali Sodium chromate, as sodium dichromate 99 raw material processed after saturated sodium dichromate solution washing, mother liquor is evaporated to further and uses as circulation alkali liquor containing more than NaOH50%.Solid liquid phase method processing condition are high temperature, high pressure, high-alkali, and long reaction time, make equipment material requirement high, technical process is long, facility investment is large, power consumption is high, and industrial scale is difficult to expand, and its reaction residual liquor magazins' layout process complexity is tediously long, Recycling Mother Solution transpiring moisture is large, the reasons such as energy consumption is high cause comprehensive cost significantly to raise, and for many years, fail to form industrially scalable.
(4) chromium hot melt thermal oxidation method production Sodium chromate main production is: ferrochrome mixes with alkali after superfine grinding pulls an oar, with being pumped in 4 ~ 22MPa autoclave, pass into oxygen simultaneously and carry out alkaline oxygenated stripping, service temperature is 150 DEG C ~ 370 DEG C, reaction residual liquor is down to normal pressure and be cooled to≤120 DEG C after carry out solid-liquid separation, filter cake and high scum, filtrate and chromic salts sodium solution.Because hydrothermal oxidization method processing condition are high temperature, high pressure, make that equipment requirements is high, investment is large, power consumption is high, be difficult to form industrial scale.In addition raw material is as being ferrochrome, and the abnormal height of product comprehensive cost as utilized by-product ferrochrome powder, then limits by raw material sources.For many years, formation industrially scalable not yet in effect.
Wall problem is tied for by the furnace charge in chromite roasting Sodium chromate process, existing Patents technical scheme is disclosed, if Chinese Patent Application No. is 201110153036.X, the applying date is on June 9th, 2011, this application case will comprise chromite, be selected from soda ash, sodium bicarbonate, compound melting liquid phase roasting at 350-1500 DEG C in the presence of oxygen in horizontal revolving kiln of one or more and optional Sodium chromate in sodium sulfate and sodium hydroxide, obtain Sodium chromate, wherein said rotary kiln comprises kiln body and is positioned at two ends at these kiln body two ends, two ends are respectively equipped with high-order liquid-phase outlet and low level liquid-phase outlet, oxygen rifle and charging opening is provided with it at kiln, wherein oxygen rifle and charging opening are crisscross arranged and make oxygen rifle and charging opening not on the same cross section of kiln body, and be positioned at kiln exhanst gas outlet with it between those parts being in closer high-order liquid-phase outlet in high-order liquid-phase outlet and charging opening and oxygen rifle.The method makes chromite be melting liquid phase in molten salt system, to some extent solves the problem that calcium-free roasting technique easily ties wall, but for the reaction conditions improving molten salt system, the shortening oxidizing roasting time still needs further improvement.
Summary of the invention
1. invent the technical problem that will solve
The object of the invention is to overcome the furnace charge ring formation (knurl) that chromite calcium-free roasting in prior art-sulfuric acid acidation legal system sodium dichromate 99 production technique exists, the problem that production efficiency is low, provide a kind of rotary kiln device of sodium dichromate production by calcium-free calcination, adopt technical scheme of the present invention, greatly improve rotary kiln productivity, shorten the oxidizing roasting time, there is good economic benefit and development prospect.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The rotary kiln device of a kind of sodium dichromate production by calcium-free calcination of the present invention, comprise kiln body, also comprise top blast tuyere device, side-blown tuyere device, bottom blowing tuyere device, feed end burner, blowing end burning device, charging opening, siphon elevated outlet, transmission mechanism, gear ring, exhanst gas outlet, siphon flue, fixing flue, end cap, slag notch and spray gun, wherein:
Described kiln body is horizontal revolving kiln, the length-to-diameter ratio of this kiln body is 3 ~ 6, described kiln body comprises feed end and blowing end, described feed end is provided with charging opening, feed end burner and exhanst gas outlet, this feed end burner is fixedly installed on end cap, and described exhanst gas outlet is connected to fixing flue by siphon flue, described blowing end is provided with siphon elevated outlet, slag notch and blowing end burning device, described blowing end burning device is fixedly installed on end cap, bottom blowing tuyere device is provided with bottom described kiln body, described kiln body two side is symmetrically arranged with side-blown tuyere device, described kiln body top is provided with top blast tuyere device, above-mentioned top blast tuyere device, side-blown tuyere device, bottom blowing tuyere device is horizontal, and be connected with spray gun respectively, this top blast tuyere device, side-blown tuyere device, the length of bottom blowing tuyere device arrangement is respectively 30 ~ 70% of kiln body length, the top blast tuyere device that distance blowing end is nearest, side-blown tuyere device, bottom blowing tuyere device is 20 ~ 50% of kiln body length to the distance of blowing end end cap, described top blast tuyere device, side-blown tuyere device, the number of bottom blowing tuyere device is 4 ~ 30, described kiln body is provided with actuating unit, and this actuating unit comprises transmission mechanism and gear ring, and described gear ring is fixed on the periphery of kiln body, and described transmission mechanism moves for driving gear ring.
Further, described top blast tuyere device, side-blown tuyere device, bottom blowing tuyere device include ball valve, sound damper and melt temperature measurer; Described spray gun is four-layer structure: innermost layer is fuel channel, and the second layer is oxygen channel, and third layer is rifle air passageways, and the 4th layer is shroud air passage, and above-mentioned spray gun axis and the axis angle of kiln body are 25 ~ 155 °.
Further, the length-to-diameter ratio of described kiln body is 4 ~ 5.
Further, the length of described top blast tuyere device, side-blown tuyere device, the arrangement of bottom blowing tuyere device is respectively 30 ~ 70% of kiln body length, a top blast tuyere device nearest apart from blowing end, side-blown tuyere device, bottom blowing tuyere device are 25 ~ 35% of kiln body length to the distance of blowing end end cap, the number of described top blast tuyere device is 4, the number of described side-blown tuyere device is 30, and the number of described bottom blowing tuyere device is 6.
3. beneficial effect
Adopt technical scheme provided by the invention, compared with existing known technology, there is following unusual effect:
(1) the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination of the present invention, the length-to-diameter ratio of its kiln body is 3 ~ 6, remarkable shortening compared with the rotary kiln being 15 ~ 20 with length-to-diameter ratio conventional in prior art, facility investment, capital cost obviously reduce, and rotary kiln of the present invention does not rotate under normal circumstances, power consumption is low; Because length-to-diameter ratio is little, make heat radiation few, heating is concentrated, and horizontal revolving kiln fuel consumption of the present invention reduces by more than 20%, and separate unit rotary kiln throughput improves 2 ~ 3 times;
(2) the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination of the present invention, the bottom of its rotary kiln, sidewall and top are provided with eye of wind device, this eye of wind device connects spray gun, blast the stirring action of gas at spray gun under, the mass-transfer efficiency of oxygen, the dispersion of material and homogenizing can be improved, oxidizing roasting time shorten more than 50%, and effectively can prevent the generation of the accident such as dross, freezing of a furnace, be conducive to fused salt to flow out, and oxidation of chromite rate reaches 98.7% ~ 99.5%.
Accompanying drawing explanation
Fig. 1 is the structural representation of the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination of the present invention;
Fig. 2 is the structural representation of spray gun in the present invention;
Fig. 3 is the cross-sectional view of spray gun in the present invention;
Fig. 4 is rotary kiln immersion side-blown in the present invention, bottom blowing, top blast fused salt flow field schematic diagram.
Label declaration in schematic diagram:
1, kiln body; 21, top blast tuyere device; 22, blow side tuyere device; 23, bottom blowing tuyere device; 31, feed end burner; 32, blowing end burning device; 4, charging opening; 5, siphon elevated outlet; 6, transmission mechanism; 7, gear ring; 8, exhanst gas outlet; 91, fuel channel; 92, oxygen channel; 93, rifle air passageways; 94, shroud air passage; 10, end cap; 11, slag notch; 12, siphon flue; 13, fixing flue.
Embodiment
For understanding content of the present invention further, the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
embodiment 1
Composition graphs 1, the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination of the present embodiment, comprises kiln body 1, top blast tuyere device 21, side-blown tuyere device 22, bottom blowing tuyere device 23, feed end burner 31, blowing end burning device 32, charging opening 4, siphon elevated outlet 5, transmission mechanism 6, gear ring 7, exhanst gas outlet 8, siphon flue 12, fixing flue 13, end cap 10, slag notch 11 and spray gun.
The kiln body 1 of the present embodiment is the horizontal revolving kiln of φ 2.15 × 9m, the length-to-diameter ratio of this kiln body 1 is 4.2, in the present invention, the length-to-diameter ratio of kiln body 1 is designed to 3 ~ 6, it is one of key improvements of the present invention point, remarkable shortening compared with the rotary kiln being 15 ~ 20 with length-to-diameter ratio conventional in prior art, make heat radiation few, heating is concentrated, make fuel consumption reduce by more than 20%, separate unit rotary kiln throughput improves 2 ~ 3 times.The kiln body 1 of the present embodiment comprises feed end and blowing end, described feed end is provided with charging opening 4, feed end burner 31 and exhanst gas outlet 8, this feed end burner 31 is fixedly installed on end cap 10, described exhanst gas outlet 8 is connected to fixing flue 13 by siphon flue 12, and charging opening 4 is arranged on the top of kiln body 1; Described blowing end is provided with siphon elevated outlet 5, slag notch 11 and blowing end burning device 32, described blowing end burning device 32 is fixedly installed on end cap 10, slag notch 11 is for blowing out under the emergency state and release slag, prevents dead stove and blowing out, and inspection used during the phase.It is particular design of the present invention that the present embodiment is provided with burner at feed end and blowing end, and when raw material are progressively put in rotary kiln, start feed end burner 31 and blowing end burning device 32, raw material are progressively melting in rotary kiln, and reaction generates fused salt.The kiln body 1 of the present embodiment is provided with actuating unit, this actuating unit comprises transmission mechanism 6 and gear ring 7, described gear ring 7 is fixed on the periphery of kiln body 1, described transmission mechanism 6 moves for driving gear ring 7, rotary kiln of the present invention does not do turning motion in normal productive process, only presses specified location rotate in blow-on phase, shutdown period.
In order to improve the mass-transfer efficiency of oxygen in rotary kiln, the dispersion of material and homogenizing, shorten the oxidizing roasting time, bottom blowing tuyere device 23 is provided with bottom the kiln body 1 of the present embodiment, described kiln body 1 two side is symmetrically arranged with side-blown tuyere device 22, described kiln body 1 top is provided with top blast tuyere device 21, above-mentioned top blast tuyere device 21, side-blown tuyere device 22, bottom blowing tuyere device 23 are horizontal, and are connected with spray gun respectively.Top blast tuyere device 21 in the present invention, side-blown tuyere device 22, the length that bottom blowing tuyere device 23 arranges is respectively 30 ~ 70% of kiln body 1 length, the top blast tuyere device 21 that distance blowing end is nearest, side-blown tuyere device 22, bottom blowing tuyere device 23 is 20 ~ 50% of kiln body 1 length to the distance of blowing end end cap 10, described top blast tuyere device 21, side-blown tuyere device 22, the number of bottom blowing tuyere device 23 is 4 ~ 30, specific as follows in the present embodiment: top blast tuyere device 21, side-blown tuyere device 22, the length that bottom blowing tuyere device 23 arranges is respectively 60% of kiln body 1 length, the top blast tuyere device 21 that distance blowing end is nearest, side-blown tuyere device 22, bottom blowing tuyere device 23 is 30% of kiln body 1 length to the distance of blowing end end cap 10, the number of described top blast tuyere device 21 is 4, the number of described side-blown tuyere device 22 is 30, these 30 side-blown tuyere devices 22 are uniformly distributed the two side being arranged in kiln body 1, the number of described bottom blowing tuyere device 23 is 6.During concrete use, can select different injection methods as required, as shown in Figure 4 (a), as shown in Figure 4 (b), the melt flow field schematic diagram of top blast as shown in Figure 4 (c) for the melt flow field schematic diagram of bottom blowing for the melt flow field schematic diagram of side-blown.
The top blast tuyere device 21 of the present embodiment, side-blown tuyere device 22, bottom blowing tuyere device 23 include ball valve, sound damper and melt temperature measurer.As shown in Figures 2 and 3; spray gun in the present embodiment is four-layer structure: innermost layer is fuel channel 91; this fuel channel 91 is for passing into coal dust and air; the second layer is oxygen channel 92, and this oxygen channel 92 is made up of 4 oxygen blades, and third layer is rifle air passageways 93; this rifle air passageways 93 is made up of 6 rifle air passageways blades; 4th layer is shroud air passage 94, and this shroud air passage 94 passes into shroud air, for the protection of spray gun.Above-mentioned spray gun axis and the axis angle of kiln body 1 are 25 ~ 155 °.
Schematically above be described the present invention and embodiment thereof, this description does not have restricted, and also just one of the embodiments of the present invention shown in accompanying drawing, actual structure is not limited thereto.So, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, designing the frame mode similar to this technical scheme and embodiment without creationary, all should protection scope of the present invention be belonged to.
Claims (3)
1. the rotary kiln device of a sodium dichromate production by calcium-free calcination, comprise kiln body (1), it is characterized in that: also comprise top blast tuyere device (21), side-blown tuyere device (22), bottom blowing tuyere device (23), feed end burner (31), blowing end burning device (32), charging opening (4), siphon elevated outlet (5), transmission mechanism (6), gear ring (7), exhanst gas outlet (8), siphon flue (12), fixing flue (13), end cap (10), slag notch (11) and spray gun, wherein:
Described kiln body (1) is horizontal revolving kiln, the length-to-diameter ratio of this kiln body (1) is 3 ~ 6, described kiln body (1) comprises feed end and blowing end, described feed end is provided with charging opening (4), feed end burner (31) and exhanst gas outlet (8), this feed end burner (31) is fixedly installed on end cap (10), and described exhanst gas outlet (8) is connected to fixing flue (13) by siphon flue (12); Described blowing end is provided with siphon elevated outlet (5), slag notch (11) and blowing end burning device (32), described blowing end burning device (32) is fixedly installed on end cap (10);
Described kiln body (1) bottom is provided with bottom blowing tuyere device (23), described kiln body (1) two side is symmetrically arranged with side-blown tuyere device (22), described kiln body (1) top is provided with top blast tuyere device (21), above-mentioned top blast tuyere device (21), side-blown tuyere device (22), bottom blowing tuyere device (23) is horizontal, and be connected with spray gun respectively, this top blast tuyere device (21), side-blown tuyere device (22), the length that bottom blowing tuyere device (23) arranges is respectively 30 ~ 70% of kiln body (1) length, the top blast tuyere device (21) that distance blowing end is nearest, side-blown tuyere device (22), bottom blowing tuyere device (23) is 20 ~ 50% of kiln body (1) length to the distance of blowing end end cap (10), described top blast tuyere device (21), side-blown tuyere device (22), the number of bottom blowing tuyere device (23) is 4 ~ 30, described top blast tuyere device (21), side-blown tuyere device (22), bottom blowing tuyere device (23) include ball valve, sound damper and melt temperature measurer, described spray gun is four-layer structure: innermost layer is fuel channel (91), the second layer is oxygen channel (92), third layer is rifle air passageways (93), 4th layer is shroud air passage (94), and the axis angle of above-mentioned spray gun axis and kiln body (1) is 25 ~ 155 °,
Described kiln body (1) is provided with actuating unit, this actuating unit comprises transmission mechanism (6) and gear ring (7), described gear ring (7) is fixed on the periphery of kiln body (1), and described transmission mechanism (6) moves for driving gear ring (7).
2. the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination according to claim 1, is characterized in that: the length-to-diameter ratio of described kiln body (1) is 4 ~ 5.
3. the rotary kiln device of a kind of sodium dichromate production by calcium-free calcination according to claim 2, it is characterized in that: described top blast tuyere device (21), side-blown tuyere device (22), the length that bottom blowing tuyere device (23) arranges is respectively 30 ~ 70% of kiln body (1) length, the top blast tuyere device (21) that distance blowing end is nearest, side-blown tuyere device (22), bottom blowing tuyere device (23) is 25 ~ 35% of kiln body (1) length to the distance of blowing end end cap (10), the number of described top blast tuyere device (21) is 4, the number of described side-blown tuyere device (22) is 30, the number of described bottom blowing tuyere device (23) is 6.
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|---|---|---|---|---|
| CN102643977A (en) * | 2011-06-09 | 2012-08-22 | 四川省安县银河建化（集团）有限公司 | Molten liquid phase roasting method of chromite |
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| CN102643977A (en) * | 2011-06-09 | 2012-08-22 | 四川省安县银河建化（集团）有限公司 | Molten liquid phase roasting method of chromite |
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