CN105598132B - A kind of method of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag - Google Patents

A kind of method of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag Download PDF

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CN105598132B
CN105598132B CN201610035340.7A CN201610035340A CN105598132B CN 105598132 B CN105598132 B CN 105598132B CN 201610035340 A CN201610035340 A CN 201610035340A CN 105598132 B CN105598132 B CN 105598132B
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blast furnace
slag
chromium slag
biomass
furnace slag
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CN105598132A (en
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张大磊
郝志鹏
李公伟
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Shanxi Wenlong Zhongmei Huanneng Technology Co ltd
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Qingdao University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B09B3/45Steam treatment, e.g. supercritical water gasification or oxidation

Abstract

The present invention is a kind of new utilization liquid steel slag crack biomass and the method for producing high-quality fuel gas.By technology controlling and process, liquid steel slag can effectively be cooled down and effectively utilize its heat energy, while converting biomass into high-quality energy gas.This process technology scheme is:By liquid steel slag heating and gasified bio-matter and cooling water, under the catalytic action of slag, with vapor catalytic reaction occurs for biomass cracking gases, and tar increasingly generates the energy gas based on CO and H2, while the Cl and CO2 in energy gas are absorbed by the alkaline matter in slag.This technique greatlys save the energy while making iron residue cool, while obtaining high-grade energy gas.

Description

A kind of method of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag
Technical field
The present invention is synchronization process chromium slag and biomass and the method for cooling down blast furnace slag, in innoxious chromium slag, is obtained While high-grade energy gas, the energy is greatlyd save, simultaneously.Belong to environmental protection and low-carbon technology field.
Background technology
Chromium slag is the accessory substance discharged in bichromate production process.Have because wherein containing water soluble hexavalent chromium greatly Toxicity, if the air storage without processing, different degrees of pollution can be caused to underground water source, river or marine site, sternly The growth being detrimental to health with animals and plants of weight.
On the whole, the detoxification of current chromium slag(The high Cr VI of toxicity is changed into trivalent chromium)It is divided into wet method detoxifcation With dry detoxified two major class.But there is respective problem.Wet method is by by adding reducing agent by Cr in chromium slag6+In liquid-phase reduction solution The method of poison.But method reagent consumption is big, and cost is high, also it is difficult at present extensive for administering chromium slag.Dry detoxified is both logical Crossing the strong reducing action of high temperature reducing atmosphere makes hexavalent chrome reduction in chromium slag be the purpose that trivalent chromium reaches removing toxic substances.Traditional is dry It is to make reducing agent with carbon that method, which is administered, and 1000 DEG C or so are heated in restoring property atmosphere poisonous Cr6+It is reduced into nontoxic Cr6 +, large-scale application, in the improvement of chromium slag, there is certain economic benefit to the method, but is polluted in processing procedure with secondary dust, And cost of investment is high, energy consumption is big.
On the other hand, China produces substantial amounts of biomass every year, and nowadays most of biomass is not utilized effectively, and is carried out Field is burned, and is formd haze, has been had a strong impact on atmospheric environment.It is a kind of biomass economy method that biomass pyrolytic, which is utilized, but Its product tar is generally difficult to utilize, the problem of also there is equipment coking.The patent of application number 2014102110190 describes one The method for reforming cracking fuel gas using sludge and biomass catalyzing is planted, biomass coke tar is converted into combustible gas by this method Method, although generate the fuel gas more easily utilized, but its CO2 content is high, poor quality;1000 DEG C or so height are needed simultaneously Temperature, energy consumption is big, and utilization rate is relatively low;In addition the method also needs to utilize CaO bases, Al2O3 base catalyst costly.
In addition, China produces substantial amounts of blast furnace slag every year, liquid blast furnace temperature is high, 1500-1700 DEG C of temperature, if energy Utilize carefully, will be valuable resource.But current few technologies effectively utilize heat energy therein.
The content of the invention
In view of the shortcomings of the prior art, the present invention is at the processing of a kind of new chromium slag, biomass and liquid blast furnace Put method.By technology controlling and process, liquid blast furnace can effectively be cooled down and effectively utilize its heat energy, while biomass is turned High-quality energy gas is turned to, and by while Cr VI is efficiently reduced in chromium slag.
This process technology scheme is:By liquid blast furnace heating and gasified bio-matter and cooling water, given up followed by danger Thing chromium slag high-temperature catalytic crack biomass cracking gas, is more thoroughly converted biomass into low under conditions of steam gasification The high temperature energy gas of molecule(H2, CO and CH4 etc.), it is to avoid the coking on chromium slag surface.And the high temperature that biomass is produced simultaneously Energy gas again heats chromium slag, while making hexavalent chrome reduction in chromium slag be trivalent chromium, low temperature chromium slag is allowed in passing to energy gas Cooled down, and the Cl and CO2 in energy gas are absorbed by the alkaline matter in chromium slag.This technique is same innoxious chromium slag When, the energy is greatlyd save, while obtaining high-grade energy gas.
The method of the present invention specifically includes following steps:
(1)The liquid blast furnace of 1500-1700 DEG C of temperature is poured onto nodulizer arrival end by slag ladle, after granulation, from going out Mouth end enters revolution reaction cooling device porch, is mixed with biomass, and by biomass pyrolytic, subsequent blast furnace slag and biomass Pyrolysis coke transports to the revolution reaction cooling device port of export, is put through cooling down water cooling heel row;Cool down the cooling water and height of blast furnace slag The continuous input quality ratio of clinker is 1:(1-8);The continuous input quality ratio of biomass and blast furnace slag is 1:(1-8);
(2)Step(1)In cooling water added from the revolution reaction cooling device port of export, spray to blast furnace slag surface is heated It is converted into vapor;Vapor then with blast furnace slag reverse flow and exchanging heat, transports to revolution reaction cooling device arrival end and life Material pyrolysis gas is mixed;Gaseous mixture is then transported to nodulizer and exchanged heat with high temperature blast furnace slag, is converted into 800-1400 DEG C of height Warm gaseous mixture;
(3)By step(2)In gaseous mixture transport to catalytic reforming furnace, the chromium slag in stove after load calcining, mixed gas adds Chromium slag inside heat carries out catalytic reforming in the range of 800-1200 DEG C, generates energy gas;
(4)Step(3)The high temperature energy gas of middle generation is subsequently input in internal heat type rotary kiln end, continuously defeated with kiln tail The chromium slag brought carries out heat exchange processing, while hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas;High temperature energy gas Temperature is reduced to after less than 250 DEG C, from rotary kiln discharge, into condensing unit, between cooling water reverse flow and occurring Connect and collected after heat exchange, condensation dehydration;High temperature chromium slag after heat exchange is discharged from rotary kiln end, into cooling device, uses cooling Water is cooled to discharge after less than 150 DEG C, while controlling cooling device air pressure inside to be higher than room using produced vapor Outer air pressure 0-30kp;The mass ratio control of the high temperature energy gas continuously generated and the chromium slag continuously inputted exists(1-8):4;
(5)Step(4)High temperature chromium slag after middle heat exchange is discharged from rotary kiln end, into cooling device, uses cooling water Discharge after less than 150 DEG C is cooled to, while controlling cooling device air pressure inside higher than outdoor using produced vapor Air pressure 0-30kp;
Compared to traditional biomass treatment method, this method has following advantage:
1. using the heating of high-temperature liquid state blast furnace slag and gasified bio-matter and cooling water, produce biomass cracking product and water Steam, is that pyrolysis product catalysis preparation high-quality energy gas creates conditions;Heat energy is taken full advantage of simultaneously, the energy is substantially increased Efficiency;
2. utilize chromium slag hazardous waste chromium slag catalysis biomass, it is to avoid while using expensive catalyst, also achieve chromium Slag it is innoxious;
3. because of the effect of high-temperature steam so that chromium slag is after reduction treatment, and surface coke content greatly reduces, be conducive to place The secondary utilization of chromium slag after reason;
4. heated and innoxious chromium slag using the high temperature energy gas produced by after catalytic reforming, while having saved extra The equipment of cooling down high-temperature gas;
5. taking full advantage of the water vapour of each stage of technique generation, without extra heat source auxiliary production steam, be conducive to Energy-conservation, while reduce the discharge of steam, it is to avoid secondary thermal pollution;
6. accessory substance CO2 generated in the energy gas that biomass catalyzing cracking is produced etc. can be by alkali such as the CaO in chromium slag Property material absorbing, improve fuel product quality;
7. chromium slag cooling device is using water cooling chromium slag is cooled down, while producing steam, aggrandizement apparatus air pressure inside hinders Only extraneous air enters system, the trivalent chromium after redox, while avoiding using extra device control air pressure.
Brief description of the drawings
Fig. 1 is process chart
Fig. 2 is nodulizer schematic diagram
Wherein 1 nodulizer entrance;At 2 cracking gases and steam entry;At 3 cracking gases and steam outlet;4 blast furnace slags are made Grain outlet;5 rotating disks
Example is embodied as follows:
(1)The liquid blast furnace of 1500-1700 DEG C of temperature is poured onto nodulizer arrival end by slag ladle, after granulation, from going out Mouth end enters revolution reaction cooling device porch, is mixed with biomass, and by biomass pyrolytic, subsequent blast furnace slag and biomass Pyrolysis coke transports to the revolution reaction cooling device port of export, is put through cooling down water cooling heel row;Cool down the cooling water and height of blast furnace slag The continuous input quality ratio of clinker is 1:2;The continuous input quality ratio of biomass and blast furnace slag is 1:2;
(2)Step(1)In cooling water added from the revolution reaction cooling device port of export, spray to blast furnace slag surface is heated It is converted into vapor;Vapor then with blast furnace slag reverse flow and exchanging heat, transports to revolution reaction cooling device arrival end and life Material pyrolysis gas is mixed;Gaseous mixture is then transported to nodulizer and exchanged heat with high temperature blast furnace slag, and the high temperature for being converted into 1000 DEG C is mixed Close gas;
(3)By step(2)In gaseous mixture transport to catalytic reforming furnace, the chromium slag in stove after load calcining, mixed gas adds Chromium slag inside heat carries out catalytic reforming in the range of 800 DEG C, generates energy gas;
(4)Step(3)The high temperature energy gas of middle generation is subsequently input in internal heat type rotary kiln end, continuously defeated with kiln tail The chromium slag brought carries out heat exchange processing, while hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas;High temperature energy gas Temperature is reduced to after less than 250 DEG C, from rotary kiln discharge, into condensing unit, between cooling water reverse flow and occurring Connect and collected after heat exchange, condensation dehydration;High temperature chromium slag after heat exchange is discharged from rotary kiln end, into cooling device, uses cooling Water is cooled to discharge after less than 150 DEG C, while controlling cooling device air pressure inside to be higher than room using produced vapor Outer air pressure 0-30kp;The mass ratio of the high temperature energy gas continuously generated and the chromium slag continuously inputted is controlled 2:1;
(5)Step(4)High temperature chromium slag after middle heat exchange is discharged from rotary kiln end, into cooling device, uses cooling water Discharge after less than 150 DEG C is cooled to, while controlling cooling device air pressure inside higher than outdoor using produced vapor Air pressure 0-30kp;
(6)Toxicity characteristic leaching procedure is carried out to chromium slag after processing using the horizontal vibration methods of national standard GB 5086.2, water solubility is measured Chromium is 0.01mg/L, is significantly less than the hazardous waste upper limit 1.5mg/L of national standard GB 5085.3;Biomass per ton produces 0.6-0.7t Energy gas, flammable Gas content is higher than 80%.
Example 2:
(1)The liquid blast furnace of 1500-1700 DEG C of temperature is poured onto nodulizer arrival end by slag ladle, after granulation, from going out Mouth end enters revolution reaction cooling device porch, is mixed with biomass, and by biomass pyrolytic, subsequent blast furnace slag and biomass Pyrolysis coke transports to the revolution reaction cooling device port of export, is put through cooling down water cooling heel row;Cool down the cooling water and height of blast furnace slag The continuous input quality ratio of clinker is 1:4;The continuous input quality ratio of biomass and blast furnace slag is 1:2;
(2)Step(1)In cooling water added from the revolution reaction cooling device port of export, spray to blast furnace slag surface is heated It is converted into vapor;Vapor then with blast furnace slag reverse flow and exchanging heat, transports to revolution reaction cooling device arrival end and life Material pyrolysis gas is mixed;Gaseous mixture is then transported to nodulizer and exchanged heat with high temperature blast furnace slag, and the high temperature for being converted into 1400 DEG C is mixed Close gas;
(3)By step(2)In gaseous mixture transport to catalytic reforming furnace, the chromium slag in stove after load calcining, mixed gas adds Chromium slag inside heat carries out catalytic reforming in the range of 800 DEG C, generates energy gas;
(4)Step(3)The high temperature energy gas of middle generation is subsequently input in internal heat type rotary kiln end, continuously defeated with kiln tail The chromium slag brought carries out heat exchange processing, while hexavalent chrome reduction in chromium slag is trivalent chromium by energy gas;High temperature energy gas Temperature is reduced to after less than 250 DEG C, from rotary kiln discharge, into condensing unit, between cooling water reverse flow and occurring Connect and collected after heat exchange, condensation dehydration;High temperature chromium slag after heat exchange is discharged from rotary kiln end, into cooling device, uses cooling Water is cooled to discharge after less than 150 DEG C, while controlling cooling device air pressure inside to be higher than room using produced vapor Outer air pressure 0-30kp;The mass ratio of the high temperature energy gas continuously generated and the chromium slag continuously inputted is controlled 1:1;
(5)Step(4)High temperature chromium slag after middle heat exchange is discharged from rotary kiln end, into cooling device, uses cooling water Discharge after less than 150 DEG C is cooled to, while controlling cooling device air pressure inside higher than outdoor using produced vapor Air pressure 0-30kp;
(6)Toxicity characteristic leaching procedure is carried out to chromium slag after processing using the horizontal vibration methods of national standard GB 5086.2, water solubility is measured Chromium is 0.01mg/L, is significantly less than the hazardous waste upper limit 1.5mg/L of national standard GB 5085.3;Biomass per ton produces 0.6-0.7t Energy gas, flammable Gas content is higher than 80%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited;Although with reference to foregoing The present invention is described in detail embodiment, for the person of ordinary skill of the art, still can be to foregoing Technical scheme described in embodiment is modified, or carries out equivalent substitution to which part technical characteristic;And these are repaiied Change or replace, the essence of appropriate technical solution is departed from the spirit and scope of claimed technical solution of the invention.

Claims (7)

1. the technology of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag, it is characterised in that including such as Lower step:
(1)The liquid blast furnace of 1500-1700 DEG C of temperature is poured onto nodulizer arrival end by slag ladle, after heat exchange granulation, from going out Mouth end enters revolution reaction cooling device porch, is mixed with biomass, and by biomass pyrolytic, subsequent blast furnace slag and biomass Pyrolysis coke transports to the revolution reaction cooling device port of export, is put through cooling down water cooling heel row;
(2)Step(1)In cooling water added from the revolution reaction cooling device port of export, spray to blast furnace slag surface is by thermal transition For vapor;Vapor then with blast furnace slag reverse flow and exchanging heat, transports to revolution reaction cooling device arrival end and biomass Pyrolysis gas mixing constitutes low-temperature mixed gas;Low-temperature mixed gas is then transported to nodulizer and exchanged heat with liquid blast furnace, is converted into 800-1400 DEG C of high-temperature gas mixture;
(3)By step(2)In high-temperature gas mixture transport to catalytic reforming furnace, the chromium slag in stove after load calcining, high-temperature gas mixture Chromium slag inside heating carries out catalytic reforming in the range of 800-1200 DEG C, generates high temperature energy gas;
(4)Step(3)The high temperature energy gas of middle generation is subsequently input in internal heat type rotary kiln end, with kiln tail continuous conveying mistake The chromium slag come carries out heat exchange processing, while hexavalent chrome reduction in chromium slag is trivalent chromium by high temperature energy gas;High temperature energy gas Temperature is reduced to after less than 250 DEG C, from rotary kiln discharge, into condensing unit, between cooling water reverse flow and occurring Connect and collected after heat exchange, condensation dehydration;
(5)Step(4)High temperature chromium slag after middle heat exchange is discharged from rotary kiln end, into cooling device, using cooling water by its Discharge after less than 150 DEG C is cooled to, while controlling cooling device air pressure inside to be higher than outdoor air pressure using produced vapor 0-30kp。
2. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that the continuous input quality ratio of the cooling water and blast furnace slag that cool down blast furnace slag is 1:(1-8).
3. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that the continuous input quality ratio of biomass and blast furnace slag is 1:(1-8).
4. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that the mass ratio control of the high temperature energy gas continuously generated and the chromium slag continuously inputted exists(1-8):4.
5. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that the cooling water of cooling blast furnace slag and the continuous input quality of biomass exist than control(0.2-5):1.
6. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that the chromium slag loaded in catalytic reforming furnace is by dolomite or Al2O3Base nano catalyst is substituted.
7. the skill of a kind of utilization blast furnace slag waste heat isochronous resources metaplasia material according to claim 1 and innoxious chromium slag Art, it is characterised in that wherein described biomass is substituted by plastics or sludge.
CN201610035340.7A 2016-01-19 2016-01-19 A kind of method of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag Active CN105598132B (en)

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CN105598132B (en) * 2016-01-19 2017-09-29 青岛理工大学 A kind of method of utilization blast furnace slag waste heat isochronous resources metaplasia material and innoxious chromium slag
CN107760383A (en) * 2017-11-13 2018-03-06 中国矿业大学(北京) Blast furnace slag waste heat catalytic pyrolysis biomass gas technology
CN113005289B (en) * 2019-12-19 2022-05-27 有研资源环境技术研究院(北京)有限公司 Method for improving zinc oxygen pressure leaching rate by using calcine waste heat and oxygen pressure leaching kettle exhaust
CN113683342B (en) * 2021-07-16 2023-01-24 清远金谷智联环保产业研究院有限公司 Method for preparing high-strength artificial board by using nickel smelting furnace slag and biomass waste
CN114590607B (en) * 2022-03-09 2024-03-19 上海电气集团股份有限公司 Slag discharging system for high-temperature ash and using method thereof

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