CN101053908A - Pyrolytic treatment method for chromium slag - Google Patents
Pyrolytic treatment method for chromium slag Download PDFInfo
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- CN101053908A CN101053908A CN 200710041125 CN200710041125A CN101053908A CN 101053908 A CN101053908 A CN 101053908A CN 200710041125 CN200710041125 CN 200710041125 CN 200710041125 A CN200710041125 A CN 200710041125A CN 101053908 A CN101053908 A CN 101053908A
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Abstract
The invention relates to a thermolysis processing process of chromium slag, using dehydration mud from municipal sewage plant as an additive. The process comprises: firstly mixing the chromium slag and the mud in proportion and sending the mixture to an external heating type tilting furnace for preheat and dry, then sending the mixture to an interior heating type pyrolyzing furnace to carry out thermolysis reaction, wherein the high temperature hot reduction gas of the interior heating type pyrolyzing furnace enters from a reduction combustion furnace, and the pyrolysis products after being reduction treated are cooled and discharged. Exhaust gas of the interior heating type pyrolyzing furnace enters the external heating type tilting furnace after mixed with air via a dilution trap to dry the mixture of the chromium slag and the mud indirectly. The invention can detoxicate the chromium slag, meanwhile, treat the mud and use energy effectively, thus has obvious economic benefits and environmental benefits.
Description
Technical field
The present invention relates to a kind of pyrolysis treating method of chromium slag, use mud as reducing agent, the reducing atmosphere that produces by pyrolyzing sludge is with hexavalent chrome reduction in the chromium slag.Belong to the chromium slag disposal technology in the field of environment protection.
Background technology
The chromium slag is the accessory substance that discharges in the bichromate production process.Have great toxicity because of wherein containing water-soluble Cr VI, if without processing and air storage, can cause in various degree pollution to underground water source, river or marine site, serious is detrimental to health and vegeto-animal growth.
On the whole, the detoxification of chromium slag (be about to the high Cr VI of toxicity and become trivalent chromium) is divided into wet method detoxifcation and dry detoxified two big classes at present.Wet method is to add reducing agent with Cr in the chromium slag with passing through
6+In the liquid-phase reduction detoxifcation, this method reagent consumption is big, and the cost height also is difficult to be used on a large scale administer the chromium slag at present.
Dry detoxified is that strong reducing action by high-temperature reductibility atmosphere makes that hexavalent chrome reduction is the purpose that trivalent chromium reaches detoxifcation in the chromium slag.Traditional dry treatment is to make reducing agent with carbon, is heated in reducing atmosphere about 1000 ℃ poisonous Cr
6+Be reduced into nontoxic Cr
3+, this method large-scale application has certain economic benefit in the improvement of chromium slag, but in the processing procedure with the secondary dust pollution, and cost of investment height, energy consumption is big.
Application number is that the patent of CN1792481 has been announced a kind of technology that sulphur carries out chromic slag dry method reduction as reducing agent of adding, and this method sprays into Cosan during roasting in rotary kiln, produce SO
2Gas is in order to reduced chromium slag.This technology detoxifying effect is better, but consumes a large amount of Cosans, and SO in the tail gas
2Very easily exceed standard.
Application number is that the patent of CN1827247 has been announced a kind of method of using the agricultural wastes rice bran as additive dry method reduced chromium slag.After rice bran and chromium slag mixed, place microwave field to carry out redox reaction,, can realize chromium residue detoxifying basically so that the hexavalent chrome reduction in the chromium slag is become trivalent chromium.Yet microwave technology is with high costs, so be difficult to be used on a large scale treatment of chromate slag.
Summary of the invention
The objective of the invention is to the defective at above-mentioned treatment of chromate slag, propose a kind of pyrolysis treating method of chromium slag, utilize sewage treatment plant's pollutant mud as additive, the mode by pyrolysis is with chromium slag reduction detoxification.Can realize the innoxious of chromium slag and mud simultaneously.
For achieving the above object, the present invention sends into the pyrolysis oven interior heat after with mud chromium slag combination drying and separates, and utilizes two rotary kiln branch the two poles of the earth heating.At first with mud with after the chromium slag mixes in proportion, send into external-heating revolving stove preheating and drying, more dried mixture is sent into the internal heat type pyrolysis oven and carries out pyrolysis.Discharge solid phase product cooling back after the pyrolysis.The hot gas of internal heat type pyrolysis oven comes from and reduces the thermal reduction gas of combustion furnace, and the thermal source of preheating and drying mixture comes from the burning again of internal-heated rotary furnace tail gas, thereby effectively realizes the recycling of the energy.
Method of the present invention specifically may further comprise the steps:
1, the broken back of chromium sizing is mixed with dewatered sludge, the mass ratio of chromium slag and dewatered sludge is 1: 0.5～2, mixture sent in the external-heating revolving stove inner core through screw feeder carry out preheating and drying, mixture time of staying in external-heating revolving stove inner core is 0.25～4 hour, makes dried mixture moisture content be lower than 5%.
2, the reduction combustion furnace is fuel with the natural gas, and coefficient of excess air is less than 1 in the control reduction combustion furnace, and the hot gas temperature that makes generation is at 500～650 ℃, oxygen content＜0.5%, and the elevated temperature heat gas of generation is introduced the internal heat type pyrolysis oven.
3, will send into the internal heat type pyrolysis oven through the mixture after the preheating of external-heating revolving stove, directly the contact temperature is that 500～650 ℃ elevated temperature heat gas carries out pyrolysis processing under the condition of anaerobic or anoxic, and the time of staying is 0.25～4 hour.Mud pyrolysis in this process is semicoke and reproducibility volatilization gas, and has realized chromium slag reduction.Carbonated product after the pyrolysis processing enters cooling device, under reducing condition, be cooled to 200 ℃ after the discharging.
4, the tail gas of internal heat type pyrolysis oven has high heating value, and part comes from the natural gas of not pyrolysis, and part comes from the escaping gas of pyrolyzing sludge process.Internal heat type pyrolysis oven discharge tail gas through dilution trap with after air mixes as thermal source, send into the outer wall of external-heating revolving stove heating rotary stove, the mixture in the contact drying rotary furnace inner core realizes that the burning of pyrolysis oven tail gas utilizes again.
Dewatered sludge of the present invention is the pollutant mud (moisture content is 60～80%) that sewage treatment plant discharges, also can comprise changing food waste, the food waste of aquatic with other various organic wastes, discarded object such as replacements such as stalk, wood chip are raiseeed in agricultural, adopt wherein one or more.
The present invention has significant beneficial effect and substantive distinguishing features:
1. the present invention uses sludge of sewage treatment plant as reducing agent, than the resource-type reducing agent of other dry method, can effectively reduce cost of material.On the other hand, mud is as sewage treatment plant's discarded object, and its handling problems is a very stubborn problem of environmental area always.And this method has been carried out minimizing and innoxious to mud effectively in detoxification chromium slag, accomplishes the treatment of wastes with processes of wastes against one another, integrated treatment.
2. reaction temperature of the present invention is 500～650 ℃, will reach 900 ℃ at least with the reaction temperature of conventional dry and compare, and can effectively cut down the consumption of energy and reduce the requirement of insulation of equipment material, thereby reduces equipment investment and operating cost.
3. the present invention's high heat value gas that the internal heat type pyrolysis oven is come out has carried out burning and has utilized, in order to the mixture of preheating and drying mud and chromium slag, thereby has saved the energy, has improved energy utilization rate.
4. compare conventional dry technology, the present invention can effectively reduce SOx, and therefore the generation of NOx and dust need not expensive exhaust gas processing device, greatly reduces equipment cost.
Description of drawings
Fig. 1 is the schematic flow sheet of the inventive method.
The specific embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.
Following examples are undertaken by flow process shown in the accompanying drawing 1.At first with the chromium slag with after mud mixes by mass ratio 1: 0.5～2, send into preheating and drying in the external-heating revolving stove, send into the internal heat type pyrolysis oven after 0.25～4 hour, the pyrolysis product cooling back discharging after 0.25～4 hour reduction is handled.The reduction combustion furnace is fuel with the natural gas, and 500～650 ℃ elevated temperature heat reducing gas of generation is introduced the internal heat type pyrolysis oven.The tail gas of internal heat type pyrolysis oven with after air mixes, enters external-heating revolving stove contact drying mixture through dilution trap.
Embodiment 1
Behind chromium sizing to 60 order, mix with dewatered sludge (moisture content 80%), the mass ratio of chromium slag and mud is 1: 0.5, mixture sent in the external-heating revolving stove inner core through screw feeder carry out preheating and drying, mixture is 0.25 hour time of staying in external-heating revolving stove inner core, makes dried mixture moisture content be lower than 5%.
The reduction combustion furnace is fuel with the natural gas, coefficient of excess air 0.9 in the control reduction combustion furnace, and the hot gas temperature of generation is about 500 ℃, oxygen content＜0.5%, the elevated temperature heat gas of generation is introduced the internal heat type pyrolysis oven.
To send into the internal heat type pyrolysis oven through the mixture after the preheating of external-heating revolving stove, and carry out pyrolysis processing at the elevated temperature heat gas of direct contact temperature about 500 ℃ under the condition of anaerobic or anoxic, the time of staying is 4 hours.Mud pyrolysis in this process is semicoke and reproducibility volatilization gas, and the two has strong reducing action under hot conditions, can be rapidly with chromium slag reduction.Carbonated product after the pyrolysis processing enters cooling device, under reducing condition, be cooled to 200 ℃ after the discharging.
Internal heat type pyrolysis oven discharge tail gas through dilution trap with after air mixes as thermal source, send into the outer wall of external-heating revolving stove heating rotary stove, the mixture in the contact drying rotary furnace inner core realizes that the burning of pyrolysis oven tail gas utilizes again.
Test result:
Use GB GB 5086.2 horizontal succusions to carry out toxicity characteristic leaching procedure, record water soluble chromium, be lower than GB GB 5085.3 hazardous waste upper limit 1.5mg/L less than 1.0mg/L to handling back chromium slag.
Embodiment 2
Behind chromium sizing to 60 order, mix with dewatered sludge (moisture content 60%), the mass ratio of chromium slag and mud is 1: 2, mixture sent in the external-heating revolving stove inner core through screw feeder carry out preheating and drying, mixture is 0.25 hour time of staying in external-heating revolving stove inner core, makes dried mixture moisture content be lower than 5%.
The reduction combustion furnace is fuel with the natural gas, coefficient of excess air 0.8 in the control reduction combustion furnace, and the hot gas temperature of generation is 650 ℃, oxygen content＜0.5%, the elevated temperature heat gas of generation is introduced the internal heat type pyrolysis oven.
To send into the internal heat type pyrolysis oven through the mixture after the preheating of external-heating revolving stove, and carry out pyrolysis processing at the elevated temperature heat gas of direct contact temperature about 500 ℃ under the condition of anaerobic or anoxic, the time of staying is 4 hours.Mud pyrolysis in this process is semicoke and reproducibility volatilization gas, and the two has strong reducing action under hot conditions, can be rapidly with chromium slag reduction.Carbonated product after the pyrolysis processing enters cooling device, under reducing condition, be cooled to 200 ℃ after the discharging.
Internal heat type pyrolysis oven discharge tail gas through dilution trap with after air mixes as thermal source, send into the outer wall of external-heating revolving stove heating rotary stove, the mixture in the contact drying rotary furnace inner core realizes that the burning of pyrolysis oven tail gas utilizes again.
Test result:
Use GB GB 5086.2 horizontal succusions to carry out toxicity characteristic leaching procedure, record water soluble chromium, be lower than GB GB 5085.3 hazardous waste upper limit 1.5mg/L less than 0.2mg/L to handling back chromium slag.
Embodiment 3
Behind chromium sizing to 60 order, mix with dewatered sludge (moisture content 60%), the mass ratio of chromium slag and mud is 1: 0.5, mixture sent in the external-heating revolving stove inner core through screw feeder carry out preheating and drying, mixture is 4 hours time of staying in external-heating revolving stove inner core, make dried mixture moisture content be lower than 5%.
The reduction combustion furnace is fuel with the natural gas, coefficient of excess air 0.8 in the control reduction combustion furnace, and the hot gas temperature of generation is 500 ℃, oxygen content＜0.5%, the elevated temperature heat gas of generation is introduced the internal heat type pyrolysis oven.
To send into the internal heat type pyrolysis oven through the mixture after the preheating of external-heating revolving stove, and carry out pyrolysis processing at the elevated temperature heat gas of direct contact temperature about 500 ℃ under the condition of anaerobic or anoxic, the time of staying is 4 hours.Mud pyrolysis in this process is semicoke and reproducibility volatilization gas, and the two has strong reducing action under hot conditions, can be rapidly with chromium slag reduction.Carbonated product after the pyrolysis processing enters cooling device, under reducing condition, be cooled to 200 ℃ after the discharging.
Internal heat type pyrolysis oven discharge tail gas through dilution trap with after air mixes as thermal source, send into the outer wall of external-heating revolving stove heating rotary stove, the mixture in the contact drying rotary furnace inner core realizes that the burning of pyrolysis oven tail gas utilizes again.
Test result:
Use GB GB 5086.2 horizontal succusions to carry out toxicity characteristic leaching procedure, record water soluble chromium, be lower than GB GB 5085.3 hazardous waste upper limit 1.5mg/L less than 1.3mg/L to handling back chromium slag.
Claims (3)
1, a kind of pyrolysis treating method of chromium slag is characterized in that may further comprise the steps:
1) the broken back of chromium sizing is mixed with dewatered sludge, the mass ratio of chromium slag and dewatered sludge is 1: 0.5～2, mixture sent in the external-heating revolving stove inner core carry out preheating and drying, mixture time of staying in external-heating revolving stove inner core is 0.25～4 hour, makes dried mixture moisture content be lower than 5%;
2) the reduction combustion furnace is fuel with the natural gas, and coefficient of excess air is less than 1 in the control reduction combustion furnace, and the hot gas temperature that makes generation is at 500～650 ℃, oxygen content＜0.5%, and the elevated temperature heat gas of generation is introduced the internal heat type pyrolysis oven;
3) will send into the internal heat type pyrolysis oven through the mixture after the preheating of external-heating revolving stove, directly the contact temperature is that 500～650 ℃ elevated temperature heat gas carries out pyrolysis processing under the condition of anaerobic or anoxic, the time of staying is 0.25～4 hour, making mud pyrolysis in this process is semicoke and reproducibility volatilization gas, realize chromium slag reduction, the carbonated product cooling back discharging after the pyrolysis processing;
4) internal heat type pyrolysis oven discharge tail gas through dilution trap with after air mixes as thermal source, send into the outer wall of external-heating revolving stove heating rotary stove, the mixture in the contact drying rotary furnace inner core realizes that the burning of pyrolysis oven tail gas utilizes again.
2, according to the pyrolysis treating method of the chromium slag of claim 1, it is characterized in that described dewatered sludge moisture content is 60～80%.
3, according to the pyrolysis treating method of the chromium slag of claim 1, it is characterized in that described dewatered sludge can use changing food waste, food waste of aquatic, agricultural poultry discarded object to replace, adopt wherein one or more.
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| CN101869908A (en) * | 2010-07-06 | 2010-10-27 | 上海交通大学 | Method for chromium residue innocent treatment by utilizing rubbish percolate |
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| CN101920087A (en) * | 2010-09-06 | 2010-12-22 | 同济大学 | Reduction and detoxification method by adopting sludge in sewage plant and chromium residue obtained by burning high temperature fume |
| CN102584172A (en) * | 2012-02-06 | 2012-07-18 | 青岛理工大学 | Method for preparing water treatment filter material by taking bottom mud and chromium slag as raw materials |
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| CN111735062B (en) * | 2020-06-29 | 2021-11-16 | 中国科学院过程工程研究所 | Low-pollution-emission sludge resource incineration method and system device |
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| CN112520968A (en) * | 2021-02-08 | 2021-03-19 | 湖南爵铭环保有限公司 | Sludge carbonization method |
| CN112520968B (en) * | 2021-02-08 | 2021-06-01 | 湖南爵铭环保有限公司 | Sludge carbonization method |
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