CN104261646B - In a kind of leather-making mud heat treatment process, the Formregelung of chromium converts and controls technique - Google Patents
In a kind of leather-making mud heat treatment process, the Formregelung of chromium converts and controls technique Download PDFInfo
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Abstract
The form transformation that the invention discloses chromium in a kind of leather-making mud heat treatment process controls technique; it is characterized in that including following operation: chromium leather-making mud will be contained as in sealable reactor; it is passed through after protective atmosphere drains oxygen; it is heated to 450～1200 DEG C; protection throughput per kilogram mud 0～20L/min; pyrolysis 10～180min; to leather-making mud, all organic matters are all pyrolyzed; stop heating; question response device is cooled to less than 150 DEG C (in order to avoid dioxygen oxidation chromium in air), takes out leather-making mud.It is an advantage of the current invention that: pyrolytic process, in leather-making mud Cr from exchangeable species, reduction-state, oxidation state these three Formregelung to residual form convert, reduce the heavy metal impact on environment；After pyrolysis, in leather-making mud mainly there is (residual form ratio >=66.67%) with residual form form in Cr, and biological effectiveness is low, and environmental risk is little；After pyrolysis, in leather-making mud, the proportions of exchangeable of Cr is reducing (< 1%), and environmental risk reduces, and according to the risk assessment factor (RAC) rating scale, it is devoid of risk to environment representation.
Description
Technical field
The invention belongs to industrial solid castoff process field, the form of chromium in a kind of leather-making mud pyrolytic process
Convert and control technique.
Background technology
Leather-making mud is a kind of solid waste of leather industry, and it is a kind of industrial sludge.Due to the process hides course of processing
Middle use Cr3+Salt is tanning agent, and its absorbance is about 70%, the Cr of about 30%3+Enter in mud with water body, so leather-making mud
Rich in chromic salt.Cr in leather-making mud3+Crops, aquatile and the mankind are all had harmful effect, meanwhile, at natural ring
Because of the change of condition, Cr in leather-making mud in border3+There is potential generation Cr6+Danger, and Cr6+Harm to environment is very
Significantly.Additionally, leather-making mud moisture is higher, content of organics is high, easily rots, gives out a foul smell, and contains one simultaneously
Fixed pathogenic microorganism, parasitic ovum etc., environment all can be caused certain pollution by these.
Heat treatment comprises burning and two kinds of processing modes of pyrolysis.Burn and typically carry out in oxygen containing atmosphere.Pyrolysis is general
Vacuum environment or non-oxygen not combustion gas atmosphere (such as: the gas such as nitrogen, argon) are carried out.
Leather-making mud is as a kind of dangerous solid waste, and its disposal technology should possess minimizing, stabilisation and innoxious feature.
Leather-making mud has combustibility.Burning can be greatly reduced the volume of leather-making mud, destroys the pathogen in leather-making mud, it is possible to
Reclaim certain heat energy.In the U.S., Japan, Europe etc., danger solid waste is all used for burning electricity generation by a lot of countries, and emerging work
Industry country is also more and more to be done so.Along with people's enhancing to environmental consciousness, the burning disposal ratio of China's leather-making mud
Regular meeting is increasing.Rich in heavy metal Cr in leather-making mud, so its safety of heavy metal Cr in burning process is necessary
Pay close attention to.
Burning can be oxygen-enriched atmosphere (in atmosphere, oxygen be enough to support the abundant burning of mud) or oxygen-containing in anoxia
Atmosphere (containing oxygen in atmosphere, but amount of oxygen is not enough to support the abundant burning of mud) is carried out.
Owing in leather-making mud, Cr content is up to 8500～25800 mg/kg (in terms of butt), and it is Cr3+。Cr3+And
Do not exist with ionic state form, but mainly to form coordination compound (complex) with collagen fiber or other protein
Presented in.This is one of leather-making mud main distinction with general city sewage and sludge or other industrial sludges.So, system
In leather sludge hot processing procedure in Changing Pattern and the city sewage and sludge of heavy metal Cr and other industrial sludge heat treatment processes
The Changing Pattern of heavy metal Cr is inconsistent.
During the burning disposal of leather-making mud, the Changing Pattern research of Cr is more.At present, mainly have following several:
(1) the oxygen-enriched burning of leather-making mud
Heat treatment process can produce slag, flying dust and flue gas.During independent or oxygen-enriched with the coal blending burning of leather-making mud, burn
Temperature is 500～900 DEG C, and Cr accumulation rate in slag is 75%～92%, and remaining is emitted in flying dust, simultaneously burning process
A part of Cr can be made3+It is oxidized to highly toxic Cr6+, improve environmental risk；In flying dust, total chromium, content of 6-valence Cr ions are above stove
Slag, illustrates that its environmental risk is higher than slag.High-temperature fusion method is used to advantageously reduce oozing of heavy metal Cr in slag and flying dust
Filter concentration.(see Fei Zhenwei. the incinerator ashes of leather-making mud and 20 ton day danger waste burning demonstration project research [D]. Hangzhou:
Zhejiang University, 2010.)
Incineration temperature and the burning time of staying are to affect the key factor of heavy metal Cr content in slag (to see M.
Bakoglu, A. Karademir, S. Ayberk. Partitioning characteristics of targeted
heavy metals in IZAYDAS hazardous waste incinerator[J]. Journal of Hazardous
Materials, 2003, B99:89-105.).Between incineration temperature 500～900 DEG C, the heavy metal Cr in leather-making mud
Volatilize and increase (see Xu-guang Jiang, Chun-yu with the increase of chloride content in the rising of temperature and mud
Li, Zhen-wei Fei, et al. Combustion characteristics of tannery sludge
andvolatilization of heavy metals in combustion[J]. J Zhejiang Univisity-
Science A (Applied Physics & Engineering), 2010,11 (7): 530-537.).
The burning of leather-making mud and coal blending is conducive to improving combustibility, and additive ratio (sees the summer 6%～30% are relatively reasonable
Phoenix is firm, Zhao Youcai, Tang Ping. and in leather-making mud incinerator ashes and burning process, heavy metal volatilization controls research [J]. environment section
Learn journal, 2011,31 (6): 1270-1276. and unfold, green filament perhaps. leather-making mud and coal mix the experimental study of burning
[J]. energy and environment, 2007,6:17-19.).(wherein chromium content is 2000mg/kg, with butt to mix burning leather-making mud
Meter) afterwards chromium content in slag increase, total chromium is 62.00mg/kg, and Cr VI is 24.60mg/kg, but total in flying dust
Chromium content is 141mg/kg, and Cr VI 53.60mg/kg(sees Yang Yutai. blended burning of coal fired boiler leather-making mud test [J].
Beijing is energy-conservation, 2000, (1): 35-36.).
(2) leather-making mud anoxia is burned
S. Swarnalatha et al. is at N2:O2=90:10(V/V) under atmosphere, use 800 DEG C of temperature that leather-making mud is carried out
Catalysis pyrolysis, pyrolytic process Cr3+It is not converted into Cr6+.The filtration properties analysis of slag shows, leaches Cr in slag3+Concentration does not surpasses
Cross 2.05mg/L.(see: (1) S. Swarnalatha, M. Arasakumari, A. Gnanamani, et al.
Solidification/stabilization of thermally-treated toxic tannery sludge[J]
.Journal of Chemical Technologyand Biotechnology, 2006, 81(7): 1307-1315.；(2)
Gong Ying compiles. the curing/stabilizing [J] of the poisonous leather-making mud of heat treatment. and western leather, 2008,30 (14): 47-53.
；(3) S. Swarnalatha, K. Ramani, A. G. Karthi, et al. Starved air combustion
solidification/stabilization of primarychemical sludge from a tannery[J].
Journal of Hazardous Materials B, 2006,137:304-313.)
The research that above leather-making mud burns shows: during burning disposal, in leather-making mud, Cr is mainly enriched in stove
In slag, it is distributed on a small quantity in flying dust.In flying dust, Cr content is higher than slag, so its environmental risk is higher than slag.It is right more than to study
The analysis of heavy metal Cr all uses full dose (i.e. total amount, lower same) to analyze, and relates to filtration properties analysis on a small quantity, is not directed to the form of Cr
Analyze.
Heavy metal is relevant with full dose on the impact of environment.But, environment is acted on by the thing of series of complex by heavy metal
Reason, chemistry and bioprocess determine, its chemical-biological activities, animal migration and toxicity depend primarily on metal existing forms.With much money
Environment table is revealed different bio-toxicities and environmental behaviour by the different shape belonged to, and the impact on environment is also different.
BCR(European Community Bureau of Reference) method is common Speciation Analysis of Heavy Metals side
Method, metal form is divided into exchangeable species, reduction-state, oxidation state and residual form by it.Heavy metal each form danger is ordered as can
Exchange state > reduction-state > oxidation state > residual form.Exchangeable species mainly can the directly metal ion of exchange adsorption or and carbonate
The metal ion that form combines, environmentally sensitive, easily discharge, animal migration is strong, can be directly utilized by biology, to environmental risk
High；The metal ion that reduction-state mainly combines with unformed iron and manganese oxides and hydrated oxide, belongs to stronger
Ionic bond combine chemical state, be difficult to be released, but may partly discharge with changes in environmental conditions, crops are existed potential
Danger, environment is had certain risk；The metal ion that oxidation state is mainly combined with organic and sulfide, the most surely
Fixed, it is difficult to be absorbed by biology, but may result in a small amount of dissolution when Soil oxidation current potential changes, can be indirect by plant
Utilize, less to environmental risk.The metal ion that residual form mainly combines with silicate mineral, crystallization ferrum magnesium oxide etc.,
General extracting method can not extract, and activity is little, and animal migration is little, is difficult to bioavailable, little to environmental risk.Therefore,
If heavy metal exists with residual form form, it is the least on the impact of environment.
The risk assessment factor (RAC) grading according to heavy metal environmental pollution, its risk assessment factor rating standard is such as
Table 1.The risk assessment factor is to account for the percentage composition of total amount according to heavy metal exchangeable species to classify.
The table 1 risk assessment factor (RAC) standard
| RAC | Sum-rate (%) shared by heavy metal exchangeable species |
| Devoid of risk | <1 |
| Low-risk | 1～10 |
| Risk | 11～30 |
| Excessive risk | 31～50 |
| High risk | >50 |
Zhou Jianfei et al. research leather-making mud individually burn or with coal blending burning disposal during the metamorphosis of Cr
Shi Faxian, the burning process of leather-making mud improves environmental risk.See Jianfei Zhou, Ya-nan Wang, Xuepin
Liao, Wenhua Zhang and Bi Shi. Effect of co-combustion of tannery sludge and
coal the migration of Cr in the bottom ash. Journal of the Society of Leather
Technologists & Chemists, 2014,98 (2): 35-41., it is embodied in:
(1) in leather-making mud, Cr more than 90% exists with more stable oxidation states, and the proportions of exchangeable of Cr is 1%
～between 5%, according to the risk assessment factor (RAC) rating scale, it is low-risk to environment representation.
(2), after leather-making mud burns, incineration temperature is the key factor affecting Cr Morphological Transitions.Burning process makes process hides
Cr in mud is more stable residual form and adventurous exchangeable species from more stable oxidation state, and this conversion exists
Certain competitive relation.It is embodied in: low temperature burns (less than 600 DEG C) and is conducive to Cr to change toward residual form from oxidation state, high
Temperature is burned (more than 600 DEG C) and is conducive to Cr to change toward exchangeable species from oxidation state.But, burning process all adds handing over of Cr
Change state ratio, improve environmental risk.In leather-making mud, Cr is promoted to the risk after burning, Gao Feng by the low-risk before burning
Danger, the most high risk.
(3) after leather-making mud burns, a part of Cr3+It is converted into Cr6+, because Cr6+Toxicity substantially than Cr3+Height, so
Say that burning process improves environmental risk.
Summary of the invention
The invention aims to the shortcoming and defect overcoming prior art to exist, and provide at a kind of leather-making mud heat
During reason, the form transformation of chromium controls technique, and it can make in heat treatment process leather-making mud Cr from oxidation state, exchangeable species
With converting to residual form of reduction-state these three Formregelung.After heat treatment, the residual form ratio of Cr in leather-making mud >=
66.67%, and proportions of exchangeable < 1%, reduce the environmental risk of leather-making mud Cr in heat treatment process.In leather-making mud, Cr is by warm
Low-risk before treatment is reduced to the devoid of risk after heat treatment, simultaneously Cr in leather-making mud3+Cr will not be converted into6+, dirty for process hides
The safe heat treatment of mud provides a kind of new method.
For achieving the above object, technical scheme is characterized in that including following operation:
Chromium leather-making mud will be contained as in sealable reactor, be passed through after protective atmosphere drains oxygen, be heated to 450～
1200 DEG C, continue to be passed through protective atmosphere, the protection throughput per kilogram mud 0～20L/min that this stage is passed through, pyrolysis 10～
180min, to leather-making mud, all organic matters are all pyrolyzed, and stop heating, and question response device is cooled to less than 150 DEG C, Yi Miankong
Dioxygen oxidation chromium in gas, takes out leather-making mud.
Arrange further be described containing chromium leather-making mud be moisture content 3%～50% containing chromium leather-making mud, it is contemplated that after
The economy of phase heating operation, the moisture content containing chromium leather-making mud is preferably controlled in less than 25%.The mummification of leather-making mud can be
Naturally dry, it is also possible to be to carry out in desiccation apparatus.(note: the moisture content of tradition leather-making mud is between 70%～80%)
The protective atmosphere being described is set further and should be non-flammable compressive gas, noble gas and non-flammable compressive gas and indifferent gas
One in the mixed gas of body.
Arrange further be described heating-up temperature be 450～1000 DEG C.
Arrange further be protection throughput be per kilogram mud 2～10L/min.
Arrange further be pyrolysis time be 30～90min.
The reactor being described is set further and is cooled to less than 100 DEG C.
The present invention pyrolysis after leather-making mud through XRD(X-x ray diffraction) analyze show, as it is shown in figure 1, Cr is with Cr2O3With
Cr5O12Form exists.It can be considered that Cr is with Cr2O3And Cr5O12Form exists.Chromic acid chromium Cr5O12It is chromium oxide Cr2O3Brilliant
The another kind of crystal form of body electronic defects, non-structural defect.Cr5O12In chromium atom have Cr(III) and Cr(VI) two kinds of valencys
State, composition can write Cr (III)2[Cr(Ⅵ)O4]3.O in its crystal2-Ion makees approximation cube Mi Dui, Cr(III) occupy O position,
Cr(VI) ion occupies T position, forms Cr(III)-O-Cr(VI) chain, this structure is relatively stable.So, leather-making mud master after pyrolysis
To exist with most stable of residual form form, and Leaching analysis is nearly no detectable Cr(VI).
It is an advantage of the current invention that:
(1) pyrolytic process, in leather-making mud Cr from exchangeable species, reduction-state, oxidation state these three Formregelung to residual
Slag state converts, and Cr is with Cr2O3And Cr5O12Form exists, and reduces the heavy metal impact on environment.Pyrolysis temperature is the highest more favourable
In to the conversion of residual form.
(2) after pyrolysis temperature is more than 450 DEG C, in leather-making mud Cr mainly with residual form form exist (residual form ratio >=
66.67%), biological effectiveness is low, and environmental risk is little.
(3), after pyrolysis, in leather-making mud, (< 1%, untreated leather-making mud is commutative in reduction for the proportions of exchangeable of Cr
State ratio is 1%～5%), environmental risk reduces, and according to the risk assessment factor (RAC) rating scale, it is calm to environment representation
Danger.
Below in conjunction with detailed description of the invention, the present invention is described further.
Accompanying drawing explanation
XRD analysis result after the pyrolysis of Fig. 1 leather-making mud.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, is served only for the present invention being further described, no
It is understood that for limiting the scope of the present invention, the technician in this field can be according to the content of foregoing invention to the present invention
Make some nonessential improvement and adjustment.
The composition of leather-making mud is sufficiently complex, and different enterprises are because of the difference processed raw material, converted products difference, production technology
The component of its leather-making muds different is also different, and same enterprise adjusts and change in season because of converted products change, production technology
The component changing its leather-making mud would also vary from.In order to preferably express the actual effect of the present invention, elite select leather-making mud
Burn and before and after pyrolysis, the metamorphosis of Cr compares.
Embodiment 1
Object: leather-making mud 1(chromium content is 10125mg/kg, in terms of butt；Moisture content about 10%), wherein each shape of Cr
State detects chromium content, Cr with ICP-OES after using BCR method continuous extraction6+Leaching concentration uses " solid waste Leaching leaching
Method sulfonitric method (HJ/T 299-2007) " method detection.
Conventional incineration method: being placed in high-temperature atmosphere furnace by leather-making mud, overall process is passed through O2(per kilogram mud 2L/
Min).It is warming up to 500 DEG C, keeps Temperature Treatment 60min.Body of heater starts cooling, and after atmosphere furnace is cooled to 150 DEG C, taking-up is burnt
G of slag sample after burning, is placed in exsiccator and is cooled to room temperature.
Method for pyrolysis of the present invention: be placed in high-temperature atmosphere furnace by leather-making mud, is first passed through N2Drain air then to start to add
Heat, the overall process of heating is passed through N2(per kilogram mud 2L/min).It is warming up to 500 DEG C, keeps Temperature Treatment 60min.Body of heater is opened
Begin to lower the temperature, after atmosphere furnace is cooled to 150 DEG C, takes out the g of slag sample after burning, be placed in exsiccator and be cooled to room temperature.
Taking g of slag sample and carry out morphological analysis and the Leaching analysis of Cr, its result is as follows:
From table 2 it can be seen that leather-making mud is at a temperature of 500 DEG C after burning disposal, Cr6+Leaching concentration be
The proportions of exchangeable of 353.95mg/L, Cr is increased to 29.14%, and according to the risk assessment factor (RAC) rating scale, it is to ring
Border shows as risk, improves environmental risk.
But, leather-making mud is at N2Under atmosphere after 500 DEG C of temperature pyrolysis, do not leach Cr6+, Cr is mainly with residual form form
Existing (ratio is 81.43%), proportions of exchangeable is 0.07%(< 1%), according to the risk assessment factor (RAC) rating scale, its
Being devoid of risk to environment representation, environmental risk reduces (compared with the untreated and leather-making mud of burning disposal).
Embodiment 2
Object: leather-making mud 1(chromium content is 10125mg/kg, in terms of butt；Moisture content about 10%), wherein each shape of Cr
State detects chromium content, Cr with ICP-OES after using BCR method continuous extraction6+Leaching concentration uses " solid waste Leaching leaching
Method sulfonitric method (HJ/T 299-2007) " method detection.
Conventional incineration method: being placed in high-temperature atmosphere furnace by leather-making mud, overall process is passed through O2(per kilogram mud 2L/
Min).It is warming up to 600 DEG C, keeps Temperature Treatment 60min.Body of heater starts cooling, and after atmosphere furnace is cooled to 150 DEG C, taking-up is burnt
G of slag sample after burning, is placed in exsiccator and is cooled to room temperature.
Method for pyrolysis of the present invention: be placed in high-temperature atmosphere furnace by leather-making mud, is first passed through N2Drain air then to start to add
Heat, the overall process of heating is passed through N2(per kilogram mud 2L/min).It is warming up to 600 DEG C, keeps Temperature Treatment 60min.Body of heater is opened
Begin to lower the temperature, after atmosphere furnace is cooled to 150 DEG C, takes out the g of slag sample after burning, be placed in exsiccator and be cooled to room temperature.
Taking g of slag sample and carry out morphological analysis and the Leaching analysis of Cr, its result is as follows:
From table 3 it can be seen that leather-making mud is at a temperature of 600 DEG C after burning disposal, Cr6+Leaching concentration be
The proportions of exchangeable of 556.80mg/L, Cr is increased to 42.45%, and according to the risk assessment factor (RAC) rating scale, it is to ring
Border shows as excessive risk, and environmental risk significantly improves.
But, leather-making mud is at N2Under atmosphere after 600 DEG C of temperature pyrolysis, do not leach Cr6+, Cr is mainly with residual form form
Existing (ratio is 94.63%), proportions of exchangeable is 0.00%(< 1%), according to the risk assessment factor (RAC) rating scale, its
Being devoid of risk to environment representation, environmental risk reduces (compared with the untreated and leather-making mud of burning disposal).
Embodiment 3
Object: leather-making mud 1(chromium content is 10125mg/kg, in terms of butt；Moisture content about 10%), wherein each shape of Cr
State detects chromium content, Cr with ICP-OES after using BCR method continuous extraction6+Leaching concentration uses " solid waste Leaching leaching
Method sulfonitric method (HJ/T 299-2007) " method detection.
Conventional incineration method: being placed in high-temperature atmosphere furnace by leather-making mud, overall process is passed through O2(per kilogram mud 2L/
Min).It is warming up to 800 DEG C, keeps Temperature Treatment 60min.Body of heater starts cooling, and after atmosphere furnace is cooled to 150 DEG C, taking-up is burnt
G of slag sample after burning, is placed in exsiccator and is cooled to room temperature.
Method for pyrolysis of the present invention: be placed in high-temperature atmosphere furnace by leather-making mud, is first passed through N2Drain air then to start to add
Heat, the overall process of heating is passed through N2(per kilogram mud 2L/min).It is warming up to 800 DEG C, keeps Temperature Treatment 60min.Body of heater is opened
Begin to lower the temperature, after atmosphere furnace is cooled to 150 DEG C, takes out the g of slag sample after burning, be placed in exsiccator and be cooled to room temperature.
Taking g of slag sample and carry out morphological analysis and the Leaching analysis of Cr, its result is as follows:
From table 4, it can be seen that leather-making mud is at a temperature of 800 DEG C after burning disposal, Cr6+Leaching concentration be
Mainly there is (ratio is increased to 73.98%) with exchangeable species form in 293.16mg/L, Cr, comments according to the risk assessment factor (RAC)
Grade standard, it is high risk to environment representation, and environmental risk significantly improves.
But, leather-making mud is at N2Under atmosphere after 800 DEG C of temperature pyrolysis, do not leach Cr6+, Cr is mainly with residual form form
Existing (ratio is 92.76%), proportions of exchangeable is 0.24%(< 1%), according to the risk assessment factor (RAC) rating scale, its
Being devoid of risk to environment representation, environmental risk reduces (compared with the untreated and leather-making mud of burning disposal).
Embodiment 4
Object: leather-making mud 1(chromium content is 10125mg/kg, in terms of butt；Moisture content about 10%), wherein each shape of Cr
State detects chromium content, Cr with ICP-OES after using BCR method continuous extraction6+Leaching concentration uses " solid waste Leaching leaching
Method sulfonitric method (HJ/T 299-2007) " method detection.
Conventional incineration method: being placed in high-temperature atmosphere furnace by leather-making mud, overall process is passed through O2(per kilogram mud 2L/
Min).It is warming up to 1000 DEG C, keeps Temperature Treatment 60min.Body of heater starts cooling, and after atmosphere furnace is cooled to 150 DEG C, taking-up is burnt
G of slag sample after burning, is placed in exsiccator and is cooled to room temperature.
Method for pyrolysis of the present invention: be placed in high-temperature atmosphere furnace by leather-making mud, is first passed through N2Drain air then to start to add
Heat, the overall process of heating is passed through N2(per kilogram mud 2L/min).It is warming up to 1000 DEG C, keeps Temperature Treatment 60min.Body of heater is opened
Begin to lower the temperature, after atmosphere furnace is cooled to 150 DEG C, takes out the g of slag sample after burning, be placed in exsiccator and be cooled to room temperature.
Taking g of slag sample and carry out morphological analysis and the Leaching analysis of Cr, its result is as follows:
As can be seen from Table 5, leather-making mud at a temperature of 1000 DEG C after burning disposal, Cr6+Leaching concentration be
Mainly there is (ratio is increased to 75.45%) with exchangeable species form in 577.69mg/L, Cr, comments according to the risk assessment factor (RAC)
Grade standard, it is high risk to environment representation, and environmental risk significantly improves.
But, leather-making mud is at N2Under atmosphere after 1000 DEG C of temperature pyrolysis, do not leach Cr6+, Cr is mainly with residual form shape
There is (ratio is 93.03%) in formula, proportions of exchangeable is 0.10%(< 1%), according to the risk assessment factor (RAC) rating scale,
It is devoid of risk to environment representation, and environmental risk reduces (compared with the untreated and leather-making mud of burning disposal).
Embodiment 5
Object: leather-making mud 2(chromium content is 18201mg/kg, in terms of butt；Moisture content about 18%), wherein each shape of Cr
State detects chromium content, Cr with ICP-OES after using BCR method continuous extraction6+Leaching concentration uses " solid waste Leaching leaching
Method sulfonitric method (HJ/T 299-2007) " method detection.
Conventional incineration method: being placed in high-temperature atmosphere furnace by leather-making mud, overall process is passed through O2(per kilogram mud 10L/
Min).It is warming up to 600 DEG C, keeps Temperature Treatment 30min.Body of heater starts cooling, and after atmosphere furnace is cooled to 100 DEG C, taking-up is burnt
G of slag sample after burning, is placed in exsiccator and is cooled to room temperature.
Method for pyrolysis of the present invention: be placed in high-temperature atmosphere furnace by leather-making mud, is first passed through Ar and drains air and then start to add
Heat, the overall process of heating is passed through Ar(per kilogram mud 10L/min).It is warming up to 600 DEG C, keeps Temperature Treatment 30min.Body of heater is opened
Begin to lower the temperature, after atmosphere furnace is cooled to 100 DEG C, takes out the g of slag sample after burning, be placed in exsiccator and be cooled to room temperature.
Taking g of slag sample and carry out morphological analysis and the Leaching analysis of Cr, its result is as follows:
As can be seen from Table 6, leather-making mud at a temperature of 600 DEG C after burning disposal, Cr6+Leaching concentration be
The proportions of exchangeable of 625.89mg/L, Cr is increased to 38.76%, and according to the risk assessment factor (RAC) rating scale, it is to ring
Border shows as excessive risk, and environmental risk significantly improves.
But, leather-making mud after 600 DEG C of temperature pyrolysis, does not leaches Cr under an ar atmosphere6+, Cr is mainly with residual form form
Existing (ratio is 95.09%), proportions of exchangeable is 0.02%(< 1%), according to the risk assessment factor (RAC) rating scale, its
Being devoid of risk to environment representation, environmental risk reduces (compared with the untreated and leather-making mud of burning disposal).
Claims (3)
1. in a leather-making mud heat treatment process, the Formregelung of chromium converts control technique, it is characterised in that include following work
Sequence:
Chromium leather-making mud will be contained be placed in sealable reactor, and be passed through after protective atmosphere drains oxygen, be heated to 450～1200
DEG C, continue to be passed through protective atmosphere, the protection throughput per kilogram mud 2～10L/min that this stage is passed through, be pyrolyzed 30～90min,
To leather-making mud, all organic matters are all pyrolyzed, and stop heating, and question response device is cooled to less than 150 DEG C, in order to avoid oxygen in air
Gas chromium oxide, the leather-making mud after taking-up pyrolysis, residual form ratio >=66.67% of Cr in the leather-making mud after this pyrolysis, can
Exchange state ratio < 1%, and with Cr2O3And Cr5O12Form exists, described containing chromium leather-making mud be moisture content 3%～50% containing chromium
Leather-making mud.
In a kind of leather-making mud heat treatment process the most according to claim 1, the Formregelung of chromium converts and controls technique, its
It is characterised by: described protective atmosphere should be the mixed gas of non-flammable compressive gas, noble gas and non-flammable compressive gas and noble gas
In one.
In a kind of leather-making mud heat treatment process the most according to claim 1, the Formregelung of chromium converts and controls technique, its
It is characterised by: described reactor is cooled to less than 100 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| IT202100008321A1 (en) * | 2021-04-01 | 2022-10-01 | Phoenix Italy Srl | METHOD OF TREATMENT OF LEATHER PROCESSING WASTE |
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| CN106045245A (en) * | 2016-07-11 | 2016-10-26 | 辽宁点石技术开发有限公司 | Method for treating chromium-containing tannery sludge and recycling chromium metal |
| CN106077067A (en) * | 2016-07-26 | 2016-11-09 | 中国科学院武汉岩土力学研究所 | A kind of mud fever that pollutes resolves prosthetic device |
| CN108375640B (en) * | 2018-05-03 | 2021-05-25 | 北京农业质量标准与检测技术研究中心 | Method for extracting form of heavy metal chromium in mushroom based on tube furnace |
| 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 |
| CN113816424A (en) * | 2021-09-23 | 2021-12-21 | 福州大学 | Method for preparing chromate by utilizing oyster shells and tannery sludge |
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