CN102191374A - Method for recycling traditional chromium residue - Google Patents
Method for recycling traditional chromium residue Download PDFInfo
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- CN102191374A CN102191374A CN2010101217578A CN201010121757A CN102191374A CN 102191374 A CN102191374 A CN 102191374A CN 2010101217578 A CN2010101217578 A CN 2010101217578A CN 201010121757 A CN201010121757 A CN 201010121757A CN 102191374 A CN102191374 A CN 102191374A
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Abstract
The invention relates to a method for recycling traditional chromium residue, in particular to a method for recycling the traditional chromium residue by replacing strong acid (hydrochloric acid or sulfuric acid) with an ammonium salt (ammonium chloride or ammonium sulfate) of the strong acid. In the method, chromium residue generated in the traditional calcium roasting production process for sodium bichromate is taken as a treatment object, ammonium salts (including ammonium chloride and ammonium sulfate) of the strong acid and reducing ferrous salts (including ferrous chloride and ferrous sulfate) are adopted to make calcium, magnesium, sodium, chromium and the like in the chromium residue form soluble chloride or sulfate, then the calcium, the magnesium and the chromium are precipitated by utilizing ammonia released by decomposing the ammonium salts and adding carbon dioxide, and are returned to the calcium roasting production process for the sodium bichromate to realize the circulation, ammonium chloride and ammonium sulfate regenerated by reacting with the chloride and the sulfate are recycled, and final slag is used as a raw material of cement after the treatment. In the method, the strong acid is not added, so the requirements on equipment materials are reduced; and the recycling of elements such as calcium, magnesium, chromium and the like greatly reduces the amount of the final slag, and greatly improves the utilization rate of traditional chromium residue raw materials.
Description
Technical field
The present invention relates to the method for traditional chromium slag resource utilization, particularly utilize strong acid ammonium salt (ammonium chloride or ammonium sulfate) to replace strong acid (hydrochloric acid or sulfuric acid) to make the method for traditional chromium slag resource utilization.
Technical background
Tradition chromium slag is meant that traditional sodium dichromate has the chromium residue that produces in the calcium baked for producing process, exceeds standard because of wherein containing sexavalent chrome and sodium and magnesium, and it is innoxious, resource utilization becomes world-famous puzzle and make.In addition, the chromium slag is very harmful to ecotope and people's life health, so the chromium slag is listed in the No.1 harmful solid waste of chemical industry for a long time.Since half a century, all drop into a large amount of human and material resources both at home and abroad and studied, proposed many novel methods, novel process, belonged to " watershed management " and " end treatment " two big classes substantially." watershed management " thinking is to reduce the generation of chromium slag or do not discharge the chromium slag by novel method, novel process, belong to cleaner production, developed " calcium-free roasting " novel process as developed countries such as the U.S., Japan before three more than ten years, the slag rate is greatly reduced, but this technology belongs to few slag discharging, do not deal with problems, the U.S. stops chromium salt production, the whole imports of product fully at present at all; " inferior fused salt " chromic salts new cleanproduction process that Chinese Academy Of Sciences Process Engineering Research Institute proposes also is typical " watershed management ", and Yima, Henan ton demonstration project realizes no slag discharging substantially, but extensive industrialization is had got long long way to go.The thinking of " end treatment " is existing chromium residue detoxifying is handled (innoxious) and comprehensive utilization (resource utilization), belongs to recycling economy.The detoxifcation of chromium slag is handled generally and can be finished voluntarily by chromium slag generation enterprise; Comprehensive utilization generally will be connected with other relevant enterprise (as cement, ironmaking, fused(calcium magnesium)phosphate, glass and ornamental brick, refractory materials etc.) and supporting, does not have economy otherwise often because of cost such as transportation and protection it is fully utilized.The traditional chrominm salt production technology of China is that the calcium roasting is arranged basically, and the chromium quantity of slag of storing up by 2003 reaches more than 450 ten thousand tons, and constantly increase with the speed above 400,000 tons every year.The chromium slag of these enormous amount can only adopt " end treatment " mode, and the method that has proposed mainly comprises dry process (the chromium slag mixes with the coal grain, the high temperature reduction roasting), (acidolysis or alkaline hydrolysis add Na in wet processing
2S, FeSO
4Deng reductive agent reduction Cr
6+), solidification method (chromium slag and FeSO
4, mineral acid and cement or pitch, lime, flyash and chemical agent etc. solidify and seal up for safekeeping), (microorganism directly reduces Cr to microbial method
6+Enzymatic process and the indirect method of microbial metabolism, complexing, flocculation etc.) and microwave method (microwave exposure detoxifcation under the reductive agent effect) etc.There are many shortcomings such as detoxifcation is not thorough, cost is high, treatment capacity is little, efficient is low in these methods, do not solve root problem.
Summary of the invention
The method that the purpose of this invention is to provide a kind of traditional chromium slag resource utilization particularly utilizes strong acid ammonium salt (ammonium chloride or ammonium sulfate) to replace strong acid (hydrochloric acid or sulfuric acid) to make the method for traditional chromium slag resource utilization.
The method of traditional chromium slag resource utilization of the present invention, be meant that with traditional sodium dichromate the chromium slag that produces in the calcium baked for producing process being arranged is process object, adopt strong acid ammonium salt (comprising ammonium chloride and ammonium sulfate) and reductibility divalent iron salt (comprising iron protochloride and ferrous sulfate), make the calcium in the chromium slag, magnesium, sodium, chromium etc. form soluble chloride or vitriol, the ammonia and the interpolation carbonic acid gas that utilize the ammonium salt decomposition to discharge again make calcium, magnesium and chromium form precipitation and returns sodium dichromate has calcium baked for producing process to realize circulation, recycle with the ammonium chloride and the ammonium sulfate of muriate and vitriol reaction regeneration, handle the back finishing slag as the cement additire raw material.
The method of traditional chromium slag resource utilization of the present invention comprises that ammonium chloride leaches with the ammonium sulfate leaching, filters (solid-liquid separation), drying, water dissolution reaction product, evaporation concentration and circulation of muriate sulfate precipitation and key steps such as ammonium chloride and ammonium sulfate reprocessing cycle:
A. at first the traditional chromium slag behind the pulverizing and jevigating is mixed (according to the total content of traditional chromium metal in the dreg oxide compound with ammonium chloride solution (mass concentration of ammonium chloride solution is preferably 20～40%) and four water iron protochlorides, the consumption of ammonium chloride be the consumption of theoretical excessive 20～50%, the four water iron protochlorides of the integral molar quantity of the metal oxide of calcium constituent, magnesium elements, sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) in traditional chromium slag be in traditional chromium slag chromic molar weight theoretical excessive 10～20%; In temperature is preferred reaction 3～5 hours under 120～160 ℃, airtight, agitation condition; Make calcium constituent, magnesium elements, sodium element and trivalent chromic ion in traditional chromium slag (trivalent chromic ion that the reduction of original trivalent chromic ion and hexavalent chromium obtains in traditional chromium slag) change into the muriate of calcium constituent, magnesium elements, sodium element and chromium element, obtain containing the mixing solutions of calcium chloride, magnesium chloride, sodium-chlor and chromium trichloride and superfluous ammonium chloride, simultaneously, the strong basicity of tradition chromium slag is decomposed ammonium chloride and is discharged ammonia (because of containing water vapor, the ammonia that contains water vapour is ammoniacal liquor after condensation); Because of the pH of above-mentioned reaction system generally in that (traditional chromium slag is strong basicity more than 4.0, ammonium chloride is slightly acidic, by operational condition of the present invention, reaction back system pH remains on more than 4.0 substantially), in the case, ferro element in the traditional chromium slag and aluminium element are stayed ammonium chloride substantially and are leached in the residue;
B. the mixing solutions that step a is obtained carries out filter operation realization solid-liquid separation, obtains containing calcium chloride, magnesium chloride, and the mixing solutions of sodium-chlor and chromium trichloride and ammonium chloride leach residue; To contain calcium chloride, magnesium chloride, (carbonic acid gas can extract from stack gas or other approach obtains for the ammoniacal liquor that the mixing solutions of sodium-chlor and chromium trichloride and step a obtain and the carbonic acid gas of interpolation, the consumption of the carbonic acid gas of ammoniacal liquor and interpolation all with respect to calcium, magnesium, sodium and chromic muriatic integral molar quantity theoretical excessive 20～30%) reaction, obtain magnesium hydrate precipitate, chromium hydroxide precipitation and precipitation of calcium carbonate, sodium-chlor is converted into the lower sodium bicarbonate of solubleness simultaneously; Filter, above-mentioned precipitation is separated (utilize the lower characteristics of the solubleness of sodium bicarbonate in ammonium chloride solution, sodium bicarbonate is separated with ammonium chloride solution) with sodium bicarbonate with the ammonium chloride solution that reaction produces;
C. the magnesium hydrate precipitate that step b is obtained, chromium hydroxide precipitation and precipitation of calcium carbonate with return sodium dichromate after sodium bicarbonate separates calcium baked for producing operation arranged, recycle; The sodium bicarbonate that obtains calcined to make soda ash; The ammonium chloride that step b is obtained returns step a, recycles;
D. the ammonium chloride that step b is obtained leaches the dry post analysis chemical constitution of residue, and mix with ammonium sulfate and iron vitriol in view of the above that (consumption of ammonium sulfate leaches integral molar quantity theoretical excessive 10～15% of the metal oxide of unreacted magnesium elements, sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) in the residue with respect to ammonium chloride, the consumption of iron vitriol is with respect to theoretical excessive about 10～15% of unreacted chromic molar weight in the residue; In temperature is 300～400 ℃ of therapeutic methods to keep the adverse qi flowing downward (ammonium sulfate decompose discharge ammonia) solid state reaction 2～4 hours, water solubilizing reaction product and carry out solid-liquid separation after obtain the mixture, finishing slag of sal epsom, sodium sulfate and chromium sulphate respectively and decompose the ammoniacal liquor that the ammonia that discharges obtains through condensation ammonium sulfate;
E. the finishing slag that steps d is obtained can send the cement mill to make the cement additire raw material, the ammoniacal liquor that the metal sulfate of gained sal epsom, sodium sulfate and chromium sulphate and steps d obtain and the carbonic acid gas of interpolation (can extract from stack gas or other approach acquisition, the consumption of ammoniacal liquor and carbonic acid gas all with respect to theoretical excessive 20～30% reactions of the integral molar quantity of sal epsom, sodium sulfate and chromium sulphate, obtains magnesium hydrate precipitate, chromium hydroxide precipitation, sodium bicarbonate and ammonium sulfate; Magnesium hydrate precipitate and chromium hydroxide precipitation with return traditional sodium dichromate after sodium bicarbonate separates calcium baked for producing process arranged; The sodium bicarbonate that obtains be can be used for calcining system soda ash; Ammoniumsulphate soln returns steps d after evaporation concentration, recycle.
The reaction of step a can be expressed by equation (1)～(5); The reaction of steps d can be expressed by equation (6)～(10):
(1)
CaO+2NH
4Cl→CaCl
2+2NH
3↑+H
2O
(2)
MgO+2NH
4Cl→MgCl
2+2NH
3↑+H
2O
(3)
NaOH+NH
4Cl→NaCl+NH
3↑+H
2O
(4)
Na
2CO
3+2NH
4Cl→2NaCl+2NH
3↑+CO
2↑+H
2O
(5)
Na
2CrO
4+3FeCl
2·4H
2O+8NH
4Cl→2NaCl+3FeCl
3+CrCl
3+8NH
3↑+16H
2O
(6)
CaO+(NH
4)
2SO
4→CaSO
4↓+2NH
3↑+H
2O
(7)
MgO+(NH
4)
2SO
4→MgSO
4+2NH
3↑+H
2O
(8)
2NaOH+(NH
4)
2SO
4→Na
2SO
4+2NH
3↑+2H
2O
(9)
Na
2CO
3+(NH
4)
2SO
4→Na
2SO
4+2NH
3↑+CO
2↑+H
2O
(10)
2Na
2CrO
4+6FeSO
4·7H
2O+8(NH
4)
2SO
4→2Na
2SO
4+3Fe
2(SO
4)
3+Cr
2(SO
4)
3+16NH
3↑+50H
2O
The reaction of step b can be expressed by equation (11)～(14); The reaction of step e can be expressed by equation (15)～(17):
(11)
MgCl
2+2NH
3+2H
2O→2NH
4Cl+Mg(OH)
2↓
(12)
CrCl
3+3NH
3+3H
2O→3NH
4Cl+Cr(OH)
3↓
(13)
CaCl
2+2NH
3+CO
2+H
2O→2NH
4Cl+CaCO
3↓
(14)
NaCl+NH
3+CO
2+H
2O→NH
4Cl+NaHCO
3↓
(15)
MgSO
4+2NH
3+2H
2O→(NH
4)
2SO
4+Mg(OH)
2↓
(16)
Cr
2(SO
4)
3+6NH
3+6H
2O→3(NH
4)
2SO
4+2Cr(OH)
3↓
(17)
Na
2SO
4+2NH
3+2CO
2+2H
2O→(NH
4)
2SO
4+2NaHCO
3↓
Chromium slag described in the present invention is meant the chromium residue that tradition has calcium roasting sodium dichromate production process to produce, and exceeds standard because of wherein containing sexavalent chrome and sodium and magnesium, and it is innoxious, resource utilization becomes world-famous puzzle and make.The present invention utilizes strong acid ammonium salt (ammonium chloride and ammonium sulfate) to replace strong acid (hydrochloric acid and sulfuric acid) to handle traditional sodium dichromate the chromium slag that produces in the calcium baked for producing process, more than 120 ℃, utilize chromium slag strong basicity decomposing ammonium chloride, utilize sexavalent chrome in the traditional chromium slag of ferrous ion (iron protochloride) reduction, make elements such as sodium, calcium, magnesium and chromium form muriate; With the ammonium chloride after the solid-liquid separation leach after the residue drying more than 300 ℃ with ammonium sulfate and ferrous sulfate generation gas-solid phase reaction, further remove magnesium and sexavalent chrome, make the content of elements such as sodium in the finishing slag, magnesium and sexavalent chrome satisfy the cement additire requirement; The ammonia and the interpolation carbonic acid gas that utilize ammonium salt (ammonium chloride and ammonium sulfate) to decomposite, make the muriate or the vitriol of elements such as calcium, magnesium and chromium form magnesium hydrate precipitate, chromium hydroxide precipitation and precipitation of calcium carbonate, return the recycle of sodium dichromate production process, sodium-chlor changes into sodium bicarbonate to be separated with ammonium chloride or ammonium sulfate, and ammonium salt is through concentrating recycle.Experimental results show that with strong acid ammonium salt ammonium chloride and ammonium sulfate be conversion medium, strong acid ammonium salt combination treatment tradition chromium slag can be realized the recycle of calcium, magnesium and chromium in the chromium slag, and the index of elements such as sodium, magnesium and sexavalent chrome satisfies the cement additire requirement in the finishing slag; Because of there not being the adding of strong acid, equipment material requires to reduce; Recycling of elements such as calcium, magnesium and chromium greatly reduced the finishing slag amount, and traditional chromium slag utilization ratio of raw materials is significantly improved, and the present invention provides novel method for the innoxious and resource utilization of the chromium slag that produces in traditional sodium dichromate production process.
The present invention is further illustrated below in conjunction with drawings and Examples.
Description of drawings
Fig. 1. the process flow diagram of the method for traditional chromium slag resource utilization of the present invention.
Fig. 2. the ammonium chloride of method of the present invention leaches the used main reaction schematic representation of apparatus of traditional chromium slag.
Fig. 3. the ammonium sulfate of method of the present invention leaches the used main reaction schematic representation of apparatus of residue (solid phase after ammonium chloride leaches).
Reference numeral
1. collector 2. condensers 3. gas bombs
4. air intake valve 5. charging valves 6. bleeder valves
7. electrically heated pressure reaction still 8. stirring arms 9. tensimeters
10. magnetic stirrer 11. thermopairs 12. program temperature controllers
13. steam generator (gas circuit insulation) 14. cartridge reactors
15. insulation cartridge type resistance furnace 16-18. material reaction ware
Embodiment
See also Fig. 2, the main reaction device synoptic diagram of this device traditional chromium slag, major parts for ammonium chloride leaches be electrically heated pressure reaction still 7 (stainless steel is made, useful volume 2L, kettle cover is detachable, by bolted, airtight can the highest withstand voltage 10MPa).
Material is added by the detachable kettle cover of described electrically heated pressure reaction still 7, and uses bolted, and is airtight; Connect power supply, open outer described program temperature controller 12 switches of described electrically heated pressure reaction still, setting program, heating together with power supply; Open described magnetic stirrer 10 switches of top, described electrically heated stress reaction kettle cover outside, adjust described stirring arm 8 rotating speeds of the inner bottom part central authorities setting of described electrically heated pressure reaction still, stir material in the described electrically heated pressure reaction still; The outer described tensimeter of installing 9 of described electrically heated stress reaction kettle cover shows the still internal pressure, and described program temperature controller 12 shows temperature in the kettle, and by described thermopair 11 controlled temperature; Described gas bomb 3 (experiment is the nitrogen steel cylinder) provides pressure (greater than the still internal pressure), to go in the still from the hydraulic pressure of described charging valve 5 through described air intake valve 4, gas is discharged in still via described bleeder valve 6, after described condenser 2 coolings, is collected by described collector 1.
See also Fig. 3, this device is the main reaction device synoptic diagram of ammonium sulfate leaching residue, and major parts is cartridge reactor 14 (kettle cover is detachable, by bolted for stainless steel making, volume 5L).
The one described cartridge reactor 14 that has kettle cover places insulation cartridge type resistance furnace 15, and provides heat by insulation cartridge type resistance furnace 15 to cartridge reactor 14; One thermopair 11 that inserts in the cartridge reactor 14 is connected by the program temperature controller 12 of lead with the external energize of described cartridge reactor kettle cover, and by the temperature of described program temperature controller 12 by described thermopair 11 control cartridge type resistance furnaces; More than one material reaction ware (can be porcelain boat) is installed in described cartridge reactor 14, and reaction mass places in the described material reaction ware; One steam generator 13 (gas circuit insulation) is connected with the pipeline that has air intake valve 4 that inserts described cartridge reactor inside, and supplies with water vapour by charging valve 4 and steam generator 13 in described cartridge reactor; One the other end that inserts the pipeline that has bleeder valve 6 of described cartridge reactor 14 inside is connected with condenser 2, condenser 2 is connected with collector 1 by pipeline, and discharge gas by cartridge reactor by described bleeder valve 6, and after described condenser 2 coolings, collect by described collector 1.
Material is added by the detachable kettle cover of described cartridge reactor 14, and uses bolted, and is airtight; Connect power supply, open described program temperature controller 12 switches, setting program, heating; Described program temperature controller 12 shows reactor temperature, and by temperature in described thermopair 11 controlling reactor; The water vapour that described producer gas generator 13 is produced is in described intake valve 4 enters into described cartridge reactor 14, the ammonia that produces in the reaction process is discharged from reactor by described bleeder valve 6 together with water vapour, after described condenser 2 coolings, absorb by described collector 1.
Above-mentioned equipment therefor is a kind of selection, does not have uniqueness and exclusiveness, also can adopt other similar devices to realize the present invention.
The traditional chromium slag that provides with Yima, Henan chromium salt factory is as raw material, and its chemical constitution is as shown in table 1.
Table 1, Yima, Henan chromium salt factory red vanadium sodium production process produce the principal element chemical constitution of chromium slag
| Element | Na | Ca | Mg | Fe | Al | Si | Cr 6+ | O | Other | Add up to |
| Wt％ | 1.54 | 20.13 | 10.01 | 9.19 | 5.33 | 9.61 | 1.48 | 36.75 | 5.96 | 100 |
| Oxide compound | Na 2O | CaO | MgO | Fe 2O 3 | Al 2O 3 | SiO 2 | Cr 2O 3 | - | Other | Add up to |
| Wt％ | 2.08 | 28.18 | 16.68 | 13.13 | 10.07 | 20.59 | 2.16 | - | 7.11 | 100 |
The method of the present invention tradition chromium slag resource utilization is leached by ammonium chloride and ammonium sulfate leaching two main processes and filtration, precipitation, drying, water-soluble, supporting processes such as evaporation concentration are formed, technical process sees also Fig. 1, and ammonium chloride leaches and ammonium sulfate leaches used reaction unit as mentioned above.
One, ammonium chloride leaches: take by weighing 100g tradition chromium slag and (cross 100 mesh sieves behind the pulverizing and jevigating, form as shown in table 1), 208g ammonium chloride and 20g four water iron protochlorides, and measure 485ml ammonium chloride that deionized water dissolving is got be made into mass concentration be 30% (this moment ammonium chloride consumption be in the traditional relatively chromium slag of consumption of theoretical excessive 20%, four water iron protochloride of the integral molar quantity of calcium constituent, magnesium elements, sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) in traditional chromium slag chromic molar weight theoretical excessive 20%).Above-mentioned whole materials are joined in the above-mentioned electrically heated pressure reaction still 7, airtight, temperature programming is carried out in control by described thermopair 11 and described program temperature controller 12, making the temperature in the electrically heated pressure reaction still is 120 ℃, the mixing speed of controlling described stirring arm 8 by described magnetic stirrer 10 is 300rpm, the gas-liquid-solid phase reaction that carries out the ammonium chloride leaching is (referring to equation (1)～(5), be gas-liquid-solid three-phase coexistence in the system this moment, gas mainly is ammonia and water vapour), reaction times is 4 hours, make the calcium constituent in traditional chromium slag, magnesium elements, sodium element and trivalent chromic ion (trivalent chromic ion that the reduction of original trivalent chromic ion and hexavalent chromium obtains in traditional chromium slag) change into calcium constituent, magnesium elements, the muriate of sodium element and chromium element, obtain containing calcium chloride, magnesium chloride, the mixing solutions of the ammonium chloride of sodium-chlor and chromium trichloride and surplus, simultaneously, the strong basicity of tradition chromium slag is decomposed ammonium chloride and is discharged ammonia (because of containing water vapor, being ammoniacal liquor after the condensation); Tensimeter 9 shows the still internal pressure, and program temperature controller 12 shows temperature in the kettle.Reach set temperature of reaction and be 120 ℃ after, be interrupted by bleeder valve 6 and discharge rare gas element in the reaction systems (when initial, have the part air of bringing into when feeding in raw material in the still), carbonic acid gas, ammonia and water vapor, by condenser 2 condensations, collector 1 water absorbs ammonia and recording volume, (this pressure changes with the still internal pressure to provide pressure by nitrogen gas steel cylinder 3 simultaneously, a little higher than still internal pressure, purpose is to overcome the still internal pressure and hydraulic pressure is gone in the still, to keep liquid-solid ratio in the still), control by described air intake valve 4 and described charging valve 5 adds entry, the water equivalent that the water yield of this adding is taken out of when discharging via bleeder valve 6 with ammonia is with the maintenance system liquid-solid ratio.After reaching 4 hours time of setting reaction, stop heating, be cooled to below 100 ℃ and normal pressure (by tensimeter 9 indications), stop to stir, open the capping of electrically heated pressure reaction still 7, discharging, filter while hot, obtain containing calcium chloride, magnesium chloride, the mixing solutions of sodium-chlor and chromium trichloride and ammonium chloride leach residue, and the ammonium chloride that adds gained behind the clear water washing and filtering leaches residue, then the ammonium chloride of gained is leached residue (filter cake) place in the loft drier 120 ℃ dry down (dry back is 65g, this moment after testing, if Na, Mg, indexs such as Cr reach requirement, this residue can be sent the cement mill to make the cement additire raw material and use, the ammonium sulfate that will carry out not up to standard leaches).(consumption of ammoniacal liquor and carbonic acid gas is all with respect to calcium to add simultaneously the ammoniacal liquor of system recoveries and carbonic acid gas in pH is 4.9 filtered liquid, magnesium, sodium and chromic muriatic integral molar quantity theoretical excessive 20～30%), make the magnesium in the filtered liquid, trivalent chromium and calcium constituent form magnesium hydrate precipitate, chromium hydroxide precipitation and precipitation of calcium carbonate are also returned the sodium dichromate production process, sodium-chlor change into low solubility sodium bicarbonate and with can remove calcining system soda ash after ammonium chloride that reaction produces separates, the ammonium chloride solution that generates in the precipitation process returns the ammonium chloride leaching process and recycles.
Two, ammonium sulfate leaches: take by weighing the above-mentioned dried ammonium chloride of 65g and leach residue (filter cake), (consumption of this ammonium sulfate leaches unreacted magnesium elements in the residue with respect to ammonium chloride to 94g ammonium sulfate, the integral molar quantity of the metal oxide of sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) theoretical excessive 10%) and 10g iron vitriol (consumption of iron vitriol is with respect to theoretical excessive 10% of unreacted chromic molar weight in the residue), the three is mixed back equivalent adding and is tiled in material reaction ware 16, in material reaction ware 17 and the material reaction ware 18, above-mentioned three material reaction wares are placed cartridge reactor 14, airtight, control by thermopair 11 and program temperature controller 12, making 15 temperature programmings of insulation cartridge type resistance furnace is 300 ℃ to temperature, carry out gas (ammonia and water vapour that ammonium sulfate leaches, referring to equation (6)～(10)) solid state reaction, the reaction times is 3 hours.Feed the discharge (via bleeder valve 6) and absorption (condenser 2 condensations, collector 1 water absorption) of water vapour (providing) by intake valve 4 after reaching 300 ℃ of temperature of setting to quicken ammonia by vapour generator 13.After reaching 3 hours reaction times of setting, stop heating, stop the water flowing steam, cooling cooling, the discharging of uncapping.The reaction product that is dissolved in water earlier refilters and adds clear water washing solid product, and filter cake is finishing slag, and constituent contents such as the sodium in this filter cake, magnesium, sexavalent chrome satisfy the cement additire requirement, can be used as system cement additire raw material and use.Simultaneously to sulfur acid magnesium, (consumption of ammonia and carbonic acid gas is all with respect to sal epsom for the ammoniacal liquor of adding system recoveries and carbonic acid gas in the filtered liquid of sodium sulfate and chromium sulphate, the integral molar quantity of sodium sulfate and chromium sulphate theoretical excessive 20～30%), make sal epsom and chromium sulphate form magnesium hydrate precipitate with chromium hydroxide precipitation (magnesium hydrate precipitate separates the back with chromium hydroxide precipitation with sodium bicarbonate) and return sodium dichromate calcium baked for producing process is arranged, the sodium bicarbonate that sodium sulfate changes into low solubility with can remove calcining system soda ash after ammoniumsulphate soln separates, ammoniumsulphate soln then returns ammonium sulfate and leaches and recycle after evaporation concentration.
The result that embodiment 1 handles 100g chromium slag is: lime carbonate, magnesium hydroxide and chromium hydroxide precipitation be 64.5g altogether, and all returning sodium dichromate has calcium baked for producing process; Finishing slag amount 53.7g, its sodium element content＜0.1% (sodium oxide content＜0.15%), magnesium element content＜0.4% (content of magnesia＜0.7%), the cement additire requirement is satisfied in sexavalent chrome constituent content＜0.05 ‰, can be used as the system cement raw material.
Adopting the method and apparatus of embodiment 1, is that different reaction conditionss is:
One, ammonium chloride leaches:
Take by weighing 100g tradition chromium slag (cross 100 mesh sieves behind the pulverizing and jevigating, form as shown in table 1), take by weighing 240g ammonium chloride and 20g four water iron protochlorides, measure deionized water 445ml.
Experiment condition: temperature of reaction be 160 ℃, ammonium chloride consumption be in the mass concentration theoretical excessive 50%, ammonium chloride solution of the integral molar quantity of the metal oxide of calcium constituent, magnesium elements, sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) in the traditional chromium slag relative traditional chromium slag of consumption that is 35%, four water iron protochlorides chromic molar weight theoretical excessive 20%), mixing speed 300rpm, reaction times is 4 hours, and all the other operations are leached identical with embodiment 1 ammonium chloride.
Experimental result: filtering filtrate pH is 4.5, and filtering the dry back of filter cake (ammonium chloride leaching residue) is 62g.
Two, ammonium sulfate leaches:
Take by weighing ammonium chloride and leach and exsiccant filter cake (ammonium chloride leaching residue) 62g, take by weighing ammonium sulfate 98g, take by weighing iron vitriol 8g.
Experiment condition is: temperature of reaction is 400 ℃, the consumption of ammonium sulfate leach with respect to ammonium chloride the metal oxide of unreacted magnesium elements, sodium element and chromium element (comprising trivalent chromium and sexavalent chrome) in the residue integral molar quantity theoretical excessive 20%, the consumption of iron vitriol is 3 hours with respect to theoretical excessive 10%, the reaction times of unreacted chromic molar weight in the residue, feed water vapour in the reaction process, all the other operations are leached identical with embodiment 1 ammonium sulfate.
The result that embodiment 2 handles 100g chromium slag is: lime carbonate, magnesium hydroxide and chromium hydroxide precipitation be 65g altogether, and all returning sodium dichromate has calcium baked for producing process; Finishing slag amount 52.3g, its sodium element content＜0.1% (sodium oxide content＜0.15%), magnesium element content＜0.4% (content of magnesia＜0.7%), the cement additire requirement is satisfied in sexavalent chrome constituent content＜0.05 ‰, can be used as the system cement raw material.
Claims (4)
1. the method for a traditional chromium slag resource utilization is characterized in that, this method may further comprise the steps:
A. at first the traditional chromium slag behind the pulverizing and jevigating is mixed with ammonium chloride solution and four water iron protochlorides, the consumption of ammonium chloride be the consumption of theoretical excessive 20～50%, the four water iron protochlorides of the integral molar quantity of the metal oxide of calcium constituent, magnesium elements, sodium element and chromium element in traditional chromium slag be in traditional chromium slag chromic molar weight theoretical excessive 10～20%; Under being 120～160 ℃, airtight, agitation condition, temperature reacts; Make calcium constituent, magnesium elements, sodium element and trivalent chromic ion in traditional chromium slag change into the muriate of calcium constituent, magnesium elements, sodium element and chromium element, obtain containing the mixing solutions of calcium chloride, magnesium chloride, sodium-chlor and chromium trichloride and superfluous ammonium chloride, simultaneously, ammonium chloride decomposes and discharges the ammonia that contains water vapour, and the ammonia that contains water vapour is ammoniacal liquor after condensation;
B. the mixing solutions that step a is obtained carries out filter operation realization solid-liquid separation, obtains containing calcium chloride, magnesium chloride, and the mixing solutions of sodium-chlor and chromium trichloride and ammonium chloride leach residue; To contain calcium chloride, magnesium chloride, the ammoniacal liquor that the mixing solutions of sodium-chlor and chromium trichloride and step a obtain and the carbon dioxide reaction of interpolation, obtain magnesium hydrate precipitate, chromium hydroxide precipitation and precipitation of calcium carbonate, sodium-chlor is converted into the lower sodium bicarbonate of solubleness simultaneously; Filter, above-mentioned precipitation is separated with the ammonium chloride solution that reaction produces with sodium bicarbonate; Wherein, the consumption of the carbonic acid gas of ammoniacal liquor and interpolation is all with respect to theoretical excessive 20～30% of calcium, magnesium, sodium and chromic muriatic integral molar quantity;
C. the magnesium hydrate precipitate that step b is obtained, chromium hydroxide precipitation and precipitation of calcium carbonate with return sodium dichromate after sodium bicarbonate separates calcium baked for producing operation arranged, recycle; The sodium bicarbonate that obtains is calcined system soda ash; The ammonium chloride that step b is obtained returns step a, recycles;
D. the ammonium chloride that step b is obtained mixes with ammonium sulfate and iron vitriol after leaching the residue drying, wherein, the consumption of ammonium sulfate leaches integral molar quantity theoretical excessive 10～15% of the metal oxide of unreacted magnesium elements, sodium element and chromium element in the residue with respect to ammonium chloride, the consumption of iron vitriol is with respect to theoretical excessive 10～15% of unreacted chromic molar weight in the residue; In temperature is to carry out gas-solid phase reaction under 300～400 ℃ 2～4 hours, water solubilizing reaction product and carry out solid-liquid separation after obtain the mixture, finishing slag of sal epsom, sodium sulfate and chromium sulphate respectively and decompose the ammoniacal liquor that the ammonia that discharges obtains through condensation ammonium sulfate;
E. the ammoniacal liquor that obtains of the metal sulfate of the sal epsom that steps d is obtained, sodium sulfate and chromium sulphate and steps d and the carbon dioxide reaction of interpolation obtain magnesium hydrate precipitate, chromium hydroxide precipitation, sodium bicarbonate and ammonium sulfate; Magnesium hydrate precipitate and chromium hydroxide precipitation with return traditional sodium dichromate after sodium bicarbonate separates calcium baked for producing process arranged; The sodium bicarbonate that obtains is used for calcining system soda ash; Ammoniumsulphate soln returns steps d after evaporation concentration, recycle; Wherein, the consumption of ammoniacal liquor and carbonic acid gas is all with respect to theoretical excessive 20～30% of the integral molar quantity of sal epsom, sodium sulfate and chromium sulphate.
2. the method for traditional chromium slag resource utilization according to claim 1 is characterized in that: the mass concentration of the described ammonium chloride solution of step a is 20～40%.
3. the method for traditional chromium slag resource utilization according to claim 1 is characterized in that: the reaction times under described airtight, the agitation condition of step a is 3～5 hours.
4. the method for traditional chromium slag resource utilization according to claim 1 is characterized in that: the finishing slag that steps d obtains send the cement mill to make the cement additire raw material.
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