CN109879616A - A kind of method of cement kiln synergic processing waste containing chromium - Google Patents
A kind of method of cement kiln synergic processing waste containing chromium Download PDFInfo
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- CN109879616A CN109879616A CN201910225293.6A CN201910225293A CN109879616A CN 109879616 A CN109879616 A CN 109879616A CN 201910225293 A CN201910225293 A CN 201910225293A CN 109879616 A CN109879616 A CN 109879616A
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Abstract
The invention discloses a kind of methods of cement kiln synergic processing waste containing chromium, the following steps are included: preceding road compatibility, three-level process for formulating, middle road control, calcining solidification and linkage surveillance, road adjusts afterwards, reduction is stablized, the preceding road compatibility is controlled by source, repeatedly homogenizing is stacked in classification, rationally add three controlling units, keep waste component containing chromium uniform, in the middle road control process, cement kiln calcining clinker lattice can solidify heavy metal ion, by the Cr cationic cure in dangerous waste into lattice, and the calcined oxide atmosphere weaker by cement kiln, reduce the ratio that Cr3+ is aoxidized to Cr6+, reduce the content of Cr6+, road adjustment is that complex reducing agent is added in cement pulverizing course after described, by the Cr6+ reduction in cement.The method of cement kiln synergic processing waste containing chromium, it is stable, it is environmentally protective, achieve the effect that solid waste decrement and energy-saving and emission-reduction, reduce the influence of the dangerous waste containing chromium, there is good Social benefit and economic benefit.
Description
Technical field
The present invention relates to cement kiln synergic processing correlative technology field, specially a kind of cement kiln synergic processing waste containing chromium
Method.
Background technique
In the industrial production, the industries such as some plating, printing and dyeing, leather metallurgy can generate more chromium residue, in waste residue
Chromium be mainly trivalent chromium and Cr VI, wherein trivalent chromium is nearly free from illeffects to human body, and Cr VI endangers to human body
Evil is very big, is easy to be lost diffusion and constitute to ecological pollution, and difficulty of governance is very big, and country's hexavalent chromium-treatments method is mainly at present
Biomaterial adsorption method, evaporation, precipitating, activated carbon adsorption, ion exchange resin, electrodialysis etc., and these methods are mainly used for
, there is processing in repairing heavy metal pollution industry object, noble metal recycling, the enrichment of metal and the heavy-metal ion removal from water body
It is difficult or expense is higher, efficiency is lower, there are secondary pollution problems, so that largely the processing of the waste material containing chromium is inconvenient.
Cement kiln synergic processing solid waste technology can utilize the multiple technologies advantage and convenience of manufacture of cement.Compared to biography
System disposal options, cement kiln synergic processing dangerous waste possesses the significant advantage of innoxious, recycling, economized, while having research table
It is bright to mix the hazardous industrial wastes containing heavy metal element (Cr, Co, Ni, Cu, Cd, Pb, Zn, As) in industrial raw material, weight
Metal ion can be dissolved into clinker lattice, and cement clinker mineral can solidify most heavy metal elements, and the solidification row
For with selectivity, this is feasible when making through cement kiln synergic processing waste material containing chromium, but excessively high heavy metal intake
Just can formation on clinker and composition generate measurable influence, be easy to make troubles to the production of cement, so that few water
Stall cooperative disposal special disposal waste material containing chromium.
In view of the above-mentioned problems, carrying out innovative design on the basis of original cement kiln synergic processing method.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of cement kiln synergic processing waste containing chromium, to solve above-mentioned background skill
It is proposed that a large amount of benefits of waste disposal containing chromium are lower in art, light water stall cooperative disposal dinectly bruning is easy to influence the product of cement
The problem of quality.
To achieve the above object, the invention provides the following technical scheme: a kind of side of cement kiln synergic processing waste containing chromium
Method, comprising the following steps: preceding road compatibility, three-level process for formulating → middle road control, calcining solidification and linkage surveillance → rear road adjustment,
Reduction is stablized；
(1) the preceding road compatibility is stacked by source control, classification is repeatedly homogenized, rationally adds three controlling units, makes
Waste component containing chromium is uniform, cooperates cement kiln synergic processing；
(2) in the middle road control process, cement kiln calcining clinker lattice can solidify heavy metal ion, will endanger
Cr cationic cure in useless is realized harmlessness disposing, and the calcined oxide atmosphere weaker by cement kiln, is reduced into lattice
The ratio that Cr3+ is aoxidized to Cr6+, local reduction atmosphere can locally realize the reduction of Cr6+, reduce the content of Cr6+；
(3) the rear road adjustment is that miberal powder, ferrous sulfate, calcium sulfite and efficiently complexing are added in cement pulverizing course
Cr6+ in cement is restored, substantially reduces the content of Cr6+ in cement by reducing agent complex reducing agent.
Preferably, the source control of the preceding road compatibility is level-one compatibility, and related personnel links up with major customer in advance, and
It is sampled to Chan Fei enterprise, carries out the plan ahead work for solid waste of marching into the arena, formulate the plan of marching into the arena, it is ensured that enter the harmful components of factory's solid waste
No more than the disposing capacity of cement kiln.
Preferably, the classification stacking of the preceding road compatibility repeatedly turns to graduation two 5, and carries out after marching into the arena, according to Cr
Solid waste is divided into high, normal, basic three classifications by constituent content, by calculating, is put in storage respectively, is then homogenized with driving grab bucket, bright
Kiln can just be entered after true regulation solid waste homogenizing, homogenization material is detected, testing result is matched and adjusted for laboratory.
Preferably, the preceding road compatibility rationally adds as graduation three 5, and needs to control to entering kiln solid waste dosage
System and calculating, are calculated by the method and standard of the national regulations such as HJ-662, GB30760, are clearly homogenized adding for solid waste
Amount, is strictly added by standard.
Preferably, the calcining solidification of the middle road control includes the following contents,
A, a degree of solid solution can be carried out in mineral facies by mixing heavy metal ion outside, and the semidiameter of Cr3+ and Fe3+ are equal
Less than 15%, replaceable formation substitutional solid solution, the ion Bauer radius of Cr3+ with it is big with Ca3+ ion Bauer semidiameter
In 15%, these cavity positions can be entered in a manner of calking and be dissolved；
B, small part Cr3+ may replace the Si4+ in dicalcium silicate and tricalcium silicate and enter mine during high-temperature calcination
Object intracell, while Cr2O3 reacts with content CaO more abundant in cement kiln and generates calcium chromate, to realize
Solidification；
C, hydration process does not cause the variation of heavy metal element coordination mode, and calcium chromate and the substituted for silicon for reacting formation are former
The Cr2O3 that son enters in lattice is mainly bonded to hydrated calcium silicate gel (C-S-H).
Preferably, the linkage surveillance of the middle road control needs to establish quality supervision system and feed-back regulatory mechanism, formulates
Water soluble chromium internal control index is in real time monitored creation data by matched Informatic Management Soft Ware in cement, finds different
Normal mechanism is reported, and adjusts produce each link parameter and solid waste addition content immediately.
Preferably, after described the reduction of road adjustment stablize need on the basis of linkage regulates and controls to the Cr VI in cement into
Row reduction, specifically includes the following aspects,
A, medicament is made using ferrous sulfate heptahydrate, miberal powder, calcium sulfite, a variety of reducing agent mix and match of solvay-type reducing agent
With to each serve as short-term substantially reduction and reduction steady in a long-term, for product category and Customer Quality requirement, tune
With different complex reducing agents, it is ensured that water soluble chromium is substantially lower than national standard and stable for extended periods of time in cement；
B, adding technology is used in combination using liquid injection, powder method for mixed addition；
C, addition point is respectively provided at by gypsum library, by cement grinding aid warehouse and at cement pulverized powder feed back pipe, wherein stone
The powdery complex reducing agent of addition point is by weighing balance weighing by cream library, then pass through into allotment library belt feeder together with gypsum into
Enter and carry out grinding in cement grinding mill, the liquid complex reducing agent of addition point passes through conveyance conduit and grinding aid by cement grinding aid warehouse
Spray into cement mill and reacted together, the powdery complex reducing agent of cement pulverized powder feed back pipe addition point by weighing balance and
Blanking scraper-trough conveyer enters from cement pulverized powder feed back pipe and carries out grinding and reaction in cement mill；
D, different composite reducing agent is added according to condition of compatibility from above three toss area respectively, and according to the condition of production
Flexible modulation complex reducing agent type and toss area, it is ensured that water soluble chromium index is far below state quota in cement products.
Compared with prior art, the beneficial effects of the present invention are: the method for cement kiln synergic processing waste containing chromium,
1, stable, it is rationally run by each link of graduation three 5, waste material containing chromium and the suitable of clinker is kept to mix
Amount avoids chromium metal intake excessively high and generates large effect, disposition amount and product quality and pre- to the formation of clinker and composition
Phase is consistent, and central control system control is stablized, and steady in a long-term to run, failure rate is low；
2, environmentally protective to achieve the effect that solid waste is reduced, which contains chromium without waste water outlet, no solid waste outlet
Solidification disposal of waste meets the needs of Chan Fei enterprise, has achieved the purpose that solid waste decrement and has handled eventually.Greatly reduce chromium residue and
The quantity in stock of chrome waste liquid produces good Social benefit and economic benefit；
3, the innate advantage of cement kiln synergic processing solid waste had both been utilized in the disposal method, burnt without introducing the new energy
Burn dangerous waste containing chromium, reduce influence to ambient enviroment, achieve the purpose that it is energy-saving, and by inorganic constituents therein for regarding
Cement producting material avoids wasting, and suitable microelement both avoids causing adverse effect to clinker, moreover it is possible to as mineralising
Agent plays facilitation to cement burning, cooperates the also original processing to Cr VI, further decreases the influence of the dangerous waste containing chromium.
Detailed description of the invention
Fig. 1 is overall flow schematic diagram of the present invention；
Fig. 2 is in level-one of embodiment of the present invention compatibility into factory's dangerous waste transfer plan and compatibility program schematic diagram；
Fig. 3 is that homogenizing matches testing result schematic diagram after single and homogenizing in graduation two of the embodiment of the present invention 5；
Fig. 4 is that solid waste dosage calculates schematic diagram in graduation three of the embodiment of the present invention 5；
Fig. 5 be the present invention in road control in produce and norm controlling schematic diagram.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of technical solution: a kind of method of cement kiln synergic processing waste containing chromium, comprising the following steps:
Preceding road compatibility, three-level process for formulating → middle road control, calcining solidification and linkage surveillance → rear road adjustment, reduction are stablized；
(1) preceding road compatibility is stacked by source control, classification is repeatedly homogenized, rationally adds three controlling units, makes containing chromium
Waste component is uniform, is convenient for cement kiln synergic processing, realizes the purpose that disposition is maximized into factory's waste containing chromium；
(2) in road control process, cement kiln calcining clinker lattice has solidification to heavy metal ion, will be in dangerous waste
Cr cationic cure into lattice, realize harmlessness disposing, and cement kiln calcining oxidizing atmosphere is weaker than other processing modes, energy
The ratio that Cr3+ is aoxidized to Cr6+ is enough reduced, local reduction atmosphere can locally realize the reduction of Cr6+, reduce containing for Cr6+
Amount；
(3) road adjustment is that miberal powder, ferrous sulfate, calcium sulfite, efficiently complexing reduction are added in cement pulverizing course afterwards
The one or more complex reducing agent such as agent, the Cr6+ in cement is restored, the content of Cr6+ in cement is substantially reduced.
The source control of the preceding road compatibility of this example is level-one compatibility, and related personnel links up with major customer in advance, and arrives and produce
Useless enterprise's sampling carries out the plan ahead work for solid waste of marching into the arena, formulates the plan of marching into the arena, it is ensured that the harmful components for entering factory's solid waste do not surpass
Cross the disposing capacity of cement kiln, the present embodiment it is as shown in Figure 1 into factory's dangerous waste transfer plan and compatibility program figure.
The classification stacking of preceding road compatibility repeatedly turns to graduation two 5, and carries out after marching into the arena, will according to Cr constituent content
Solid waste is divided into high, normal, basic three classifications, by calculating, is put in storage, is then homogenized with driving grab bucket, clear stipulaties solid waste respectively
Kiln can just be entered after homogenizing, homogenization material is detected, testing result is matched and adjusted for laboratory, and the homogenizing of the present embodiment is matched
Than testing result figure after single and homogenizing as shown in Figure 1, the present embodiment is 5000t/d production line, chlorinity control exists in homogenizing storehouse
1.0%-1.5%, chromium content control is in 4000ppm hereinafter, can just enter kiln after solid waste homogenizing, the solid waste data after homogenizing are first examined
It surveys, kiln can just then be entered by compatibility calculating.
Preceding road compatibility rationally adds as graduation three 5, and needs to be controlled and calculated to entering kiln solid waste dosage, leads to
The method and standard for crossing the national regulations such as HJ-662, GB30760 are calculated, and the dosage of solid waste is clearly homogenized, stringent by mark
Standard is added, it is ensured that product quality is controlled, and the solid waste dosage calculating figure of the present embodiment is as shown in Figure 1, the present embodiment is fallen into a trap
Calculation formula is addition content=raw material amount * (state's scale value-background values)/(measured value-state's scale value), calculates canonical reference HJ-662, GB-
30485, using Cl, Cr as Con trolling index, the two is taken to calculate the minimum value in dosage to suggest dosage.
The calcining solidification of middle road control includes the following contents,
A, a degree of solid solution can be carried out in mineral facies by mixing heavy metal ion outside, and the semidiameter of Cr3+ and Fe3+ are equal
Less than 15%, replaceable formation substitutional solid solution, the ion Bauer radius of Cr3+ with it is big with Ca3+ ion Bauer semidiameter
In 15%, these cavity positions can be entered in a manner of calking and be dissolved；
B, small part Cr3+ may replace the Si4+ in dicalcium silicate and tricalcium silicate and enter mine during high-temperature calcination
Object intracell, while Cr2O3 reacts with content CaO more abundant in cement kiln and generates calcium chromate, to realize
Solidification；
C, hydration process does not cause the variation of heavy metal element coordination mode, and calcium chromate and the substituted for silicon for reacting formation are former
The Cr2O3 that son enters in lattice is mainly bonded to hydrated calcium silicate gel (C-S-H).
The linkage surveillance of middle road control needs to establish quality supervision system and feed-back regulatory mechanism, formulates water-soluble in cement
Chromium internal control index is in real time monitored creation data by matched Informatic Management Soft Ware, and the mechanism that notes abnormalities is reported,
And it adjusts produce each link parameter and solid waste addition content immediately.
The reduction of road adjustment, which is stablized, afterwards needs to restore the Cr VI in cement on the basis of linking regulation, specifically
Including the following aspects,
A, medicament is made using ferrous sulfate heptahydrate, miberal powder, calcium sulfite, a variety of reducing agent mix and match of solvay-type reducing agent
With to each serve as short-term substantially reduction and reduction steady in a long-term, for product category and Customer Quality requirement, tune
With different complex reducing agents, it is ensured that water soluble chromium is substantially lower than national standard and stable for extended periods of time in cement；
B, adding technology is used in combination using liquid injection, powder method for mixed addition；
C, addition point is respectively provided at by gypsum library, by cement grinding aid warehouse and at cement pulverized powder feed back pipe, wherein stone
The powdery complex reducing agent of addition point is by weighing balance weighing by cream library, then pass through into allotment library belt feeder together with gypsum into
Enter and carry out grinding in cement grinding mill, the liquid complex reducing agent of addition point passes through conveyance conduit and grinding aid by cement grinding aid warehouse
Spray into cement mill and reacted together, the powdery complex reducing agent of cement pulverized powder feed back pipe addition point by weighing balance and
Blanking scraper-trough conveyer enters from cement pulverized powder feed back pipe and carries out grinding and reaction in cement mill；
D, different composite reducing agent is added according to condition of compatibility from above three toss area respectively, and according to the condition of production
Flexible modulation complex reducing agent type and toss area, it is ensured that water soluble chromium index is far below state quota in cement products.
The content being not described in detail in this specification belongs to the prior art well known to professional and technical personnel in the field.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of method of cement kiln synergic processing waste containing chromium, which comprises the following steps: preceding road compatibility, three-level
Process for formulating → middle road control, calcining solidification and linkage surveillance → rear road adjustment, reduction are stablized；
(1) the preceding road compatibility is stacked by source control, classification is repeatedly homogenized, rationally adds three controlling units, makes containing chromium
Waste component is uniform, cooperates cement kiln synergic processing；
(2) in the middle road control process, cement kiln calcining clinker lattice can solidify heavy metal ion, will be in dangerous waste
Cr cationic cure realize harmlessness disposing into lattice, and by the weaker calcined oxide atmosphere of cement kiln, reduce Cr3+ to
The ratio of Cr6+ oxidation, local reduction atmosphere can locally realize the reduction of Cr6+, reduce the content of Cr6+；
(3) the rear road adjustment is that miberal powder, ferrous sulfate, calcium sulfite and efficient complexing are added in cement pulverizing course to restore
Cr6+ in cement is restored, substantially reduces the content of Cr6+ in cement by agent complex reducing agent.
2. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: the preceding road
The source control of compatibility is level-one compatibility, and related personnel links up with major customer in advance, and samples to Chan Fei enterprise, carries out and marches into the arena
The plan ahead of solid waste works, and formulates the plan of marching into the arena, it is ensured that the harmful components for entering factory's solid waste are no more than the disposing capacity of cement kiln.
3. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: the preceding road
The classification stacking of compatibility repeatedly turns to graduation two 5, and carries out after marching into the arena, and solid waste is divided into senior middle school according to Cr constituent content
Low three classifications are put in storage respectively, are then homogenized with driving grab bucket, can just be entered after clear stipulaties solid waste homogenizing by calculating
Kiln detects homogenization material, and testing result is matched and adjusted for laboratory.
4. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: the preceding road
Compatibility rationally adds as graduation three 5, and needs to be controlled and calculated to entering kiln solid waste dosage, by HJ-662,
The method and standard of the national regulations such as GB30760 are calculated, and are clearly homogenized the dosage of solid waste, are strictly thrown by standard
Add.
5. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: the middle road
The calcining solidification of control includes the following contents,
A, a degree of solid solution can be carried out in mineral facies by mixing heavy metal ion outside, and the semidiameter of Cr3+ and Fe3+ are respectively less than
15%, replaceable formation substitutional solid solution, the ion Bauer radius of Cr3+ is all larger than with Ca3+ ion Bauer semidiameter
15%, these cavity positions can be entered in a manner of calking and be dissolved；
B, small part Cr3+ may replace the Si4+ in dicalcium silicate and tricalcium silicate and enter mineral crystalline substance during high-temperature calcination
Inside lattice, while Cr2O3 reacts with content CaO more abundant in cement kiln and generates calcium chromate, to realize solidification；
C, hydration process does not cause the variation of heavy metal element coordination mode, react formation calcium chromate and substitution silicon atom into
Enter the Cr2O3 in lattice and is mainly bonded to hydrated calcium silicate gel (C-S-H).
6. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: the middle road
The linkage surveillance of control needs to establish quality supervision system and feed-back regulatory mechanism, formulates water soluble chromium internal control index in cement,
By matched Informatic Management Soft Ware, creation data is monitored in real time, the mechanism that notes abnormalities is reported, and adjusts life immediately
Produce each link parameter and solid waste addition content.
7. a kind of method of cement kiln synergic processing waste containing chromium according to claim 1, it is characterised in that: road after described
The reduction of adjustment, which is stablized, to be needed to restore the Cr VI in cement on the basis of linking regulation, is specifically included following
Aspect,
A, medicament is used using ferrous sulfate heptahydrate, miberal powder, calcium sulfite, a variety of reducing agent mix and match of solvay-type reducing agent,
To each serve as short-term substantially reduction and reduction steady in a long-term, for product category and Customer Quality requirement, allotment
Different complex reducing agent, it is ensured that water soluble chromium is substantially lower than national standard and stable for extended periods of time in cement；
B, adding technology is used in combination using liquid injection, powder method for mixed addition；
C, addition point is respectively provided at by gypsum library, by cement grinding aid warehouse and at cement pulverized powder feed back pipe, wherein gypsum library
The powdery complex reducing agent of side addition point is weighed by weighing balance, is then passed through and is entered water together with gypsum into allotment library belt feeder
Grinding is carried out in mud mill, the liquid complex reducing agent of addition point is by conveyance conduit together with grinding aid by cement grinding aid warehouse
It sprays into cement mill and is reacted, the powdery complex reducing agent of cement pulverized powder feed back pipe addition point passes through weighing balance and blanking
Scraper-trough conveyer enters from cement pulverized powder feed back pipe and carries out grinding and reaction in cement mill；
D, different composite reducing agent is added according to condition of compatibility from above three toss area respectively, and flexible according to the condition of production
Adjust complex reducing agent type and toss area, it is ensured that water soluble chromium index is far below state quota in cement products.
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| CN111689703A (en) * | 2020-06-15 | 2020-09-22 | 浙江红狮环保股份有限公司 | Method for cooperatively treating inorganic hazardous waste in cement kiln |
| CN114060827A (en) * | 2021-11-15 | 2022-02-18 | 贵港台泥东园环保科技有限公司 | Compatibility method and device for cooperatively disposing hazardous wastes in cement kiln |
| CN115215565A (en) * | 2022-08-24 | 2022-10-21 | 常州大学 | Method for inhibiting Cr (III) oxidation in process of cooperatively treating chromium-containing solid waste by cement kiln |
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| CN111689703A (en) * | 2020-06-15 | 2020-09-22 | 浙江红狮环保股份有限公司 | Method for cooperatively treating inorganic hazardous waste in cement kiln |
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| CN115215565A (en) * | 2022-08-24 | 2022-10-21 | 常州大学 | Method for inhibiting Cr (III) oxidation in process of cooperatively treating chromium-containing solid waste by cement kiln |
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