CN105537244A - Technology for synchronously recycling biomass and enabling chromium slag to be harmless by steel slag waste heat - Google Patents
Technology for synchronously recycling biomass and enabling chromium slag to be harmless by steel slag waste heat Download PDFInfo
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- CN105537244A CN105537244A CN201610035692.2A CN201610035692A CN105537244A CN 105537244 A CN105537244 A CN 105537244A CN 201610035692 A CN201610035692 A CN 201610035692A CN 105537244 A CN105537244 A CN 105537244A
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- slag
- chromium
- chromium slag
- living beings
- energy gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
- B09B3/45—Steam treatment, e.g. supercritical water gasification or oxidation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
Abstract
The invention provides a method for synchronously processing liquid steel slag, chromium slag and biomass. The method comprises the steps that biomass is heated and gasified by the steel slag; then catalysts such as hazardous wastes and chromium slag are used for catalyzing and pyrolyzing the biomass at a high temperature; the biomass is converted to be high-temperature low-molecule energy gas thoroughly under the gasifying condition of water vapor, and coking of the surface of the chromium slag is avoided; meanwhile, the high-temperature energy gas is used for heating the chromium slag to enable hexavalent chromium in the chromium slag to be reduced to trivalent chromium; the energy gas is cooled by the way; and CO2 and Cl in the energy gas are absorbed by alkaline substances in the chromium slag. According to the technology, while the chromium slag is made harmless and the steel slag is cooled, energy is greatly saved, and meanwhile high-grade energy gas is obtained.
Description
Technical field
The present invention synchronously processes chromium slag and living beings and the method made iron residue cool, innoxious chromium slag, obtain high-grade energy gas while, greatly saved the energy, simultaneously.Belong to environmental protection and low-carbon technology field.
Background technology
Chromium slag is the accessory substance discharged in bichromate production process.Because of wherein containing water soluble hexavalent chromium and have great toxicity, if the air storage without process, can cause pollution in various degree to underground water source, river or marine site, serious is detrimental to health and vegeto-animal growth.
On the whole, the detoxification (Cr VI high by toxicity becomes trivalent chromium) of current chromium slag is divided into wet method detoxifcation and dry detoxified two large classes.But there is respective problem.Wet method adds reducing agent by Cr in chromium slag by passing through
6+in the method for liquid-phase reduction removing toxic substances.But this method reagent consumption is large, and cost is high, be also difficult to extensive for administering chromium slag at present.Dry detoxified is make hexavalent chrome reduction in chromium slag be the object that trivalent chromium reaches removing toxic substances by the strong reducing action of high-temperature reductibility atmosphere.Traditional dry treatment makees reducing agent with carbon, is heated to about 1000 DEG C poisonous Cr in restoring property atmosphere
6+be reduced into nontoxic Cr
6 +, this method large-scale application, in the improvement of chromium slag, has certain economic benefit, but pollutes with secondary dust in processing procedure, and cost of investment is high, and energy consumption is large.
On the other hand, China produces a large amount of living beings every year, and nowadays most of living beings effectively do not utilize, and carry out field burning, define haze, has had a strong impact on atmospheric environment.It is a kind of biomass economy method that biomass pyrolytic utilizes, but its product tar is difficult to utilize usually, also there is the problem of equipment coking.Application number 2014102110190 patent describes a kind of method utilizing mud and biomass catalyzing reformation cracking fuel gas, biomass coke tar is converted into the method for combustible gas by the method, although create the fuel gas comparatively easily utilized, its CO2 content is high, poor quality; Need about 1000 DEG C high temperature, energy consumption is large, and utilization rate is lower simultaneously; In addition this method also needs to utilize CaO base costly, Al2O3 catalyst based.
In addition, China produces a large amount of slags every year, and liquid steel slag temperature is high, temperature 1500-1700 DEG C, if the good good utilisation of energy, will be valuable resource.But there be limited evidence currently of has technology effectively to be utilized by heat energy wherein.
Summary of the invention
For the deficiencies in the prior art, the present invention is a kind of process method of disposal of novel chromium slag, living beings and liquid steel slag.By technology controlling and process, its heat energy effectively can be utilized by liquid steel slag effective cooling, be high-quality energy gas by biomass conversion simultaneously, and by while in chromium slag, Cr VI efficiently reduces.
This process technology scheme is: by liquid steel slag heating also gasified bio-matter and cooling water, utilize hazardous waste chromium slag high-temperature catalytic crack biomass cracking gas subsequently, be low molecular high temperature energy gas (H2, CO and CH4 etc.) by biomass conversion comparatively thoroughly under the condition of steam gasification, avoid the coking on chromium slag surface.And chromium slag heats by the high temperature energy gas that living beings produce simultaneously, make hexavalent chrome reduction in chromium slag be trivalent chromium simultaneously, allow low temperature chromium slag cool energy gas in passing, and Cl and CO2 in energy gas is absorbed by the alkaline matter in chromium slag.This technique, while innoxious chromium slag, has saved the energy greatly, obtains high-grade energy gas simultaneously.
Method of the present invention specifically comprises the following steps:
(1) liquid steel slag of temperature 1500-1700 DEG C is poured onto nodulizer arrival end by slag ladle, after granulation, revolution reaction cooling device porch is entered from the port of export, mix with living beings, and by biomass pyrolytic, slag and biomass pyrolytic coke are transported to turn round and are reacted the cooling device port of export subsequently, discharge after water quench; The cooling water made iron residue cool is 1:(1-8 with the continuous input quality ratio of slag); Living beings are 1:(1-8 with the continuous input quality ratio of slag);
(2) cooling water in step (1) adds from the revolution reaction cooling device port of export, and spray is heated to slag surface and is converted into steam; Steam, subsequently with slag reverse flow and heat exchange, is transported to revolution reaction cooling device arrival end and is mixed with pyrolysis gas of biomass; Gaseous mixture transports to nodulizer subsequently and high-temperature steel slag carries out heat exchange, is converted into the high-temperature gas mixture of 800-1400 DEG C;
(3) gaseous mixture in step (2) is transported to catalytic reforming furnace, the chromium slag after the calcining of stove internal burden, the chromium slag of mist heating the inside carries out catalytic reforming within the scope of 800-1200 DEG C, generates energy gas;
(4) the high temperature energy gas generated in step (3) inputs in internal heat type rotary kiln end subsequently, and the chromium slag of coming with kiln tail continus convergence carries out heat exchange process, and hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas simultaneously; High temperature energy gas temperature is reduced to after below 250 DEG C, discharges, enter condensing unit from rotary kiln, with cooling water reverse flow, indirect heat exchange occurs, collects after condensation dehydration; High temperature chromium slag after heat exchange is discharged from rotary kiln end, enters cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously; The high temperature energy gas of continuous generation controls at (1-8) with the mass ratio of the chromium slag inputted continuously: 4;
(5) the high temperature chromium slag in step (4) after heat exchange is discharged from rotary kiln end, enter cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously;
Compare traditional biomass treatment method, this method has following advantage:
1. utilize high-temperature liquid state slag to heat and gasified bio-matter and cooling water, produce biomass cracking product and steam, prepare high-quality energy gas for pyrolysis product catalysis and create conditions; Take full advantage of heat energy simultaneously, substantially increase energy efficiency;
2. utilize chromium slag hazardous waste chromium slag catalysis biomass, while avoiding using expensive catalyst, also achieve the innoxious of chromium slag;
3. because of the effect of high-temperature steam, make chromium slag after reduction treatment, surperficial coke content greatly reduces, and the secondary being conducive to processing rear chromium slag utilizes;
4. the high temperature energy gas produced after utilizing catalytic reforming heats and innoxious chromium slag, has saved the equipment of extra cooling down high-temperature gas simultaneously;
5. take full advantage of the water vapour that each stage of technique produces, need not extra heat source supplement production steam, be conducive to energy-conservation, decrease the discharge of steam simultaneously, avoid second heat and pollute;
6. the accessory substance CO2 etc. generated in the energy gas that biomass catalyzing cracking produces can be absorbed by alkaline matters such as the CaO in chromium slag, improves fuel product quality;
7. chromium slag cooling device utilizes water quench chromium slag, and while producing steam, aggrandizement apparatus air pressure inside, stops extraneous air to enter system, the trivalent chromium after redox, avoids simultaneously and uses extra device to control air pressure.
Accompanying drawing explanation
Fig. 1 is process chart
Fig. 2 is nodulizer schematic diagram
Wherein 1 nodulizer entrance; 2 cracking gases and steam entry place; 3 cracking gases and steam outlet place; 4 slag granulation outlets; 5 rotating discs
Concrete embodiment is as follows:
(1) liquid steel slag of temperature 1500-1700 DEG C is poured onto nodulizer arrival end by slag ladle, after granulation, revolution reaction cooling device porch is entered from the port of export, mix with living beings, and by biomass pyrolytic, slag and biomass pyrolytic coke are transported to turn round and are reacted the cooling device port of export subsequently, discharge after water quench; The cooling water made iron residue cool is 1:2 with the continuous input quality ratio of slag; Living beings are 1:2 with the continuous input quality ratio of slag;
(2) cooling water in step (1) adds from the revolution reaction cooling device port of export, and spray is heated to slag surface and is converted into steam; Steam, subsequently with slag reverse flow and heat exchange, is transported to revolution reaction cooling device arrival end and is mixed with pyrolysis gas of biomass; Gaseous mixture transports to nodulizer subsequently and high-temperature steel slag carries out heat exchange, is converted into the high-temperature gas mixture of 1000 DEG C;
(3) gaseous mixture in step (2) is transported to catalytic reforming furnace, the chromium slag after the calcining of stove internal burden, the chromium slag of mist heating the inside carries out catalytic reforming within the scope of 800 DEG C, generates energy gas;
(4) the high temperature energy gas generated in step (3) inputs in internal heat type rotary kiln end subsequently, and the chromium slag of coming with kiln tail continus convergence carries out heat exchange process, and hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas simultaneously; High temperature energy gas temperature is reduced to after below 250 DEG C, discharges, enter condensing unit from rotary kiln, with cooling water reverse flow, indirect heat exchange occurs, collects after condensation dehydration; High temperature chromium slag after heat exchange is discharged from rotary kiln end, enters cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously; The high temperature energy gas of continuous generation controls at 2:1 with the mass ratio of the chromium slag inputted continuously;
(5) the high temperature chromium slag in step (4) after heat exchange is discharged from rotary kiln end, enter cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously;
(6) use GB GB5086.2 horizontal vibration method to carry out toxicity characteristic leaching procedure to chromium slag after process, recording water soluble chromium is 0.01mg/L, is significantly less than GB GB5085.3 hazardous waste upper limit 1.5mg/L; Living beings per ton produce 0.6-0.7t energy gas, and combustible gas content is higher than 80%.
Example 2:
(1) liquid steel slag of temperature 1500-1700 DEG C is poured onto nodulizer arrival end by slag ladle, after granulation, revolution reaction cooling device porch is entered from the port of export, mix with living beings, and by biomass pyrolytic, slag and biomass pyrolytic coke are transported to turn round and are reacted the cooling device port of export subsequently, discharge after water quench; The cooling water made iron residue cool is 1:4 with the continuous input quality ratio of slag; Living beings are 1:2 with the continuous input quality ratio of slag;
(2) cooling water in step (1) adds from the revolution reaction cooling device port of export, and spray is heated to slag surface and is converted into steam; Steam, subsequently with slag reverse flow and heat exchange, is transported to revolution reaction cooling device arrival end and is mixed with pyrolysis gas of biomass; Gaseous mixture transports to nodulizer subsequently and high-temperature steel slag carries out heat exchange, is converted into the high-temperature gas mixture of 1400 DEG C;
(3) gaseous mixture in step (2) is transported to catalytic reforming furnace, the chromium slag after the calcining of stove internal burden, the chromium slag of mist heating the inside carries out catalytic reforming within the scope of 800 DEG C, generates energy gas;
(4) the high temperature energy gas generated in step (3) inputs in internal heat type rotary kiln end subsequently, and the chromium slag of coming with kiln tail continus convergence carries out heat exchange process, and hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas simultaneously; High temperature energy gas temperature is reduced to after below 250 DEG C, discharges, enter condensing unit from rotary kiln, with cooling water reverse flow, indirect heat exchange occurs, collects after condensation dehydration; High temperature chromium slag after heat exchange is discharged from rotary kiln end, enters cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously; The high temperature energy gas of continuous generation controls at 1:1 with the mass ratio of the chromium slag inputted continuously;
(5) the high temperature chromium slag in step (4) after heat exchange is discharged from rotary kiln end, enter cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously;
(6) use GB GB5086.2 horizontal vibration method to carry out toxicity characteristic leaching procedure to chromium slag after process, recording water soluble chromium is 0.01mg/L, is significantly less than GB GB5085.3 hazardous waste upper limit 1.5mg/L; Living beings per ton produce 0.6-0.7t energy gas, and combustible gas content is higher than 80%.
Above embodiment only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.
Claims (7)
1. utilize a technology for steel slag waste heat isochronous resources living beings and innoxious chromium slag, it is characterized in that, comprise the steps:
(1) liquid steel slag of temperature 1500-1700 DEG C is poured onto nodulizer arrival end by slag ladle, after heat exchange granulation, revolution reaction cooling device porch is entered from the port of export, mix with living beings, and by biomass pyrolytic, slag and biomass pyrolytic coke are transported to turn round and are reacted the cooling device port of export subsequently, discharge after water quench;
(2) cooling water in step (1) adds from the revolution reaction cooling device port of export, and spray is heated to slag surface and is converted into steam; Steam, subsequently with slag reverse flow and heat exchange, is transported to revolution reaction cooling device arrival end and is mixed with pyrolysis gas of biomass; Gaseous mixture transports to nodulizer subsequently and liquid steel slag carries out heat exchange, is converted into the high-temperature gas mixture of 800-1400 DEG C;
(3) gaseous mixture in step (2) is transported to catalytic reforming furnace, the chromium slag after the calcining of stove internal burden, the chromium slag of mist heating the inside carries out catalytic reforming within the scope of 800-1200 DEG C, generates energy gas;
(4) the high temperature energy gas generated in step (3) inputs in internal heat type rotary kiln end subsequently, and the chromium slag of coming with kiln tail continus convergence carries out heat exchange process, and hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas simultaneously; High temperature energy gas temperature is reduced to after below 250 DEG C, discharges, enter condensing unit from rotary kiln, with cooling water reverse flow, indirect heat exchange occurs, collects after condensation dehydration;
(5) the high temperature chromium slag in step (4) after heat exchange is discharged from rotary kiln end, enter cooling device, discharge after using cooling water to be cooled to less than 150 DEG C, utilizes the steam controlled cooling model device air pressure inside produced higher than outdoor air pressure 0-30kp simultaneously.
2. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, the cooling water made iron residue cool is 1:(1-8 with the continuous input quality ratio of slag).
3. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, living beings are 1:(1-8 with the continuous input quality ratio of slag).
4. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, the high temperature energy gas produced continuously controls at (1-8) with the mass ratio of the chromium slag inputted continuously: 4.
5. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, the cooling water made iron residue cool controls at (0.2-5) with the continuous input quality ratio of living beings: 1.
6. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, the chromium slag of load in catalytic reforming furnace can be substituted by dolomite, Al2O3 base nano catalyst.
7. a kind of technology utilizing steel slag waste heat isochronous resources living beings and innoxious chromium slag according to claim 1, is characterized in that, wherein said living beings can be substituted by the material containing organic principle such as plastics, mud.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017125012A1 (en) * | 2016-01-19 | 2017-07-27 | 青岛理工大学 | Method and system for synchronously recycling biomass and detoxifying chromium slag by using waste heat of blast furnace slag |
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| US5204073A (en) * | 1991-04-29 | 1993-04-20 | Guangzhou Zhufeng Institute | Toxicity elimination and comprehensive utilization of chrome residues |
| US5395601A (en) * | 1991-04-09 | 1995-03-07 | Qi-Jiang Situ | Re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues |
| CN101869908A (en) * | 2010-07-06 | 2010-10-27 | 上海交通大学 | Method for chromium residue innocent treatment by utilizing rubbish percolate |
| CN101898019A (en) * | 2010-08-13 | 2010-12-01 | 上海交通大学 | Treatment method for decontaminating chromic slag by utilizing eutrophicated algal residue |
| CN103978007A (en) * | 2013-10-28 | 2014-08-13 | 青岛理工大学 | Fluidized bed type of harmless chromium slag pyrolysis process |
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- 2016-01-19 CN CN201610035692.2A patent/CN105537244B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395601A (en) * | 1991-04-09 | 1995-03-07 | Qi-Jiang Situ | Re-calcination and extraction process for the detoxification and comprehensive utilization of chromic residues |
| US5204073A (en) * | 1991-04-29 | 1993-04-20 | Guangzhou Zhufeng Institute | Toxicity elimination and comprehensive utilization of chrome residues |
| CN101869908A (en) * | 2010-07-06 | 2010-10-27 | 上海交通大学 | Method for chromium residue innocent treatment by utilizing rubbish percolate |
| CN101898019A (en) * | 2010-08-13 | 2010-12-01 | 上海交通大学 | Treatment method for decontaminating chromic slag by utilizing eutrophicated algal residue |
| CN103978007A (en) * | 2013-10-28 | 2014-08-13 | 青岛理工大学 | Fluidized bed type of harmless chromium slag pyrolysis process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017125012A1 (en) * | 2016-01-19 | 2017-07-27 | 青岛理工大学 | Method and system for synchronously recycling biomass and detoxifying chromium slag by using waste heat of blast furnace slag |
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