CN108218025A - The method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes - Google Patents
The method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes Download PDFInfo
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- CN108218025A CN108218025A CN201711277304.2A CN201711277304A CN108218025A CN 108218025 A CN108218025 A CN 108218025A CN 201711277304 A CN201711277304 A CN 201711277304A CN 108218025 A CN108218025 A CN 108218025A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
A kind of generated the invention discloses steel industry pickling the metal hydroxides sludge that is generated after liquid caustic soda neutralizes of nitration mixture waste water and add the calcirm-fluoride mud resource recycling method generated after calcium chloride solution, it is main to include adding liquid caustic soda generation after carrying out reduction by nitration mixture waste water, by being obtained after the concentration of ultra micro seperator and filter press press filtration（Solid content 50%）Metal hydroxides sludge and by ultra micro seperator production water generated after adding calcium chloride, obtained after precipitation concentration press filtration（Solid content 50%）The recycling of calcium fluoride sludge can recycle metal values ion and calcium fluoride sludge in pickling nitration mixture waste water, do not generate harmful dangerous solid waste, turn waste into wealth, and improve the economic benefit of sewage disposal, reduce cost of disposal.
Description
Technical field
The sludge treatment field that the invention belongs to be generated after environmental protection wastewater treatment, particularly a kind of steel industry pickling
The metal hydroxides sludge and add the fluorination generated after calcium chloride solution that the nitration mixture waste water of generation generates after liquid caustic soda neutralizes
The recoverying and utilizing method of calcium mud resource.
Background technology
With the fast development of China's process economics, the fast development of steel industry is driven, steel original paper is in cold rolling, electricity
To remove the oxide on surface, pickling waste waters will be generated, pickling waste waters main component is SO through overpickling before plating, spraying4 2-、
H+、Fe2+、Na+、Cr6+、F-、Men+、Ni2+Deng pickling waste waters generally can be divided into neutral salt waste water and nitration mixture waste water, and wherein nitration mixture gives up
Major pollutants in water are：Fe2+、F-、Men+、Ni2+Deng.
It is existing processing nitration mixture waste water method mainly using " lime neutralization+precipitation+lime/hydrochloric acid/PAC+ secondary precipitations+
Filtering ", after having main steps that waste water enters regulating reservoir, neutralization pond is promoted to pump, adds NaOH/ lime, by PH adjust to
8-9, the metal ions such as iron, chromium, nickel reaction generation hydroxide precipitation, fluorine ion forms calcium fluoride precipitate, subsequently into precipitation
Pond carries out mud-water separation, and the sludge of generation is transported outward after sludge dehydrating and drying as dangerous solid waste to be disposed, and supernatant leads to
It crosses feeding lime, hydrochloric acid and PAC etc. and carries out smart fluorine removal, it is ensured that water outlet fluorine ion removes residual after below 10mg/L into sand filter
The suspended matter stayed, final outflow water qualified discharge.
It was verified that " lime neutralization+precipitation+lime/hydrochloric acid/PAC+ secondary precipitations+filtering " of the prior art is combined
Technique has the following disadvantages：
(1) sludge quantity is big, and sludge composition is complicated, and recycling is difficult, and non-renewable utilization, harmfulness is big, sludge mainly by
The compositions such as hydroxide precipitation, superfluous lime, calcirm-fluoride, pulverized limestone impurity, PAC/PAM medicaments water (accounting for about 50%~65%)；
The content of valuable metal salt is very low, and substantially without freshening, recovery value, more impurity makes sludge yield very with moisture
Greatly, and due to the presence (such as chromium compound) of heavy metal, such sludge has been put into hazardous solid waste list.Metal hydrogen-oxygen
Compound sludge is mixed with calcium fluoride sludge, it is difficult to be recycled.
(2) landfill stabilization of sludge causes the waste of metals resources and the destruction of environment, and the sludge containing acid, chrome waste water contains
There is the metal values substance such as a large amount of iron, chromium, nickel, carry out landfill stabilization, not only need to spend at the dangerous solid waste of great number
Expense is put, and also needs to occupy a large amount of land resource and be filled, the life of nearby residents and the water of underground water can be influenced
Matter.
Invention content
In order to overcome the problems of the above-mentioned prior art, generated the purpose of the present invention is to provide a kind of pickling of metal
The recoverying and utilizing method of nitration mixture waste water can recycle metal values ion and calcium fluoride sludge in pickling nitration mixture waste water, not produce
Raw harmful dangerous solid waste, turns waste into wealth, and improves the economic benefit of sewage disposal, reduces cost of disposal.
The recoverying and utilizing method of nitration mixture waste water that a kind of pickling of metal of the present invention generates, which is characterized in that including
Following steps：
A) the nitration mixture waste water that metal industry pickling generates is discharged into regulating reservoir, is then promoted in neutralization chamber through pump, in
Divide two-stage with slot, every grade adds in liquid caustic soda and adjusts PH, and wherein level-one neutralization chamber PH controls exist：5-6；Two level neutralization chamber PH is controlled
：7.5-8.5；
B) waste water after neutralizing is introduced into heavy metal sewage sludge circulatory pool, carries out preliminary separation of solid and liquid；
C) the top turbid of solid-liquid separation is promoted into introducing ultra micro seperator through pump and is filtered concentration, the clear liquid filtered out
Ultra micro discharge bay is discharged into, the dope filtered out is flowed back into heavy metal sewage sludge circulatory pool, continues to detach；
D) heavy metal sewage sludge circulatory pool base sludge is periodically discharged into through pump in heavy metal-polluted mud thickener, and it is (poly- to add PAM
Acrylamide) promote flocks, filter-press dehydration is then carried out by plate and frame filter press, obtains metal hydroxides sludge；It again will pressure
Supernatant is (dirty in filtrate (concentration basin sludge is press-filtered out the water come after filter press filter-press dehydration) and heavy metal-polluted mud thickener
The water that mud thickener overflows after having expired) it is discharged into sludge circulation pond；
E) metal hydroxides sludge enters drying oven and is dried, and at 150~200 DEG C, material dries for drying temperature control
Dry time control obtains metal mud in 30min~60min；
F) the metal mud obtained after drying and the raw material mix dispensing used in smelting stainless steel, reach into after stove requirement, into
Blast furnace or the direct smelting stainless steel of electric furnace；
G) waste water in ultra micro discharge bay is promoted through pump into level-one fluorine reaction tank, and level-one fluorine reaction tank is divided to two lattice, respectively
Carry out reaction fluorine removal by adding calcium chloride, water outlet enters level-one fluorine sedimentation basin and carries out mud-water separation, the supernatant isolated into
Enter level-one fluorine clear water reserviors；
H) waste water in level-one fluorine clear water reserviors is promoted through pump into two level fluorine reaction tank, and two level fluorine reaction tank is divided to two lattice, point
Reaction fluorine removal is not carried out by adding calcium chloride, PAC (aluminium polychloride) and PAM (polyacrylamide), water outlet enters two level fluorine
Sedimentation basin carries out mud-water separation；
I) supernatant isolated enters two level fluorine clear water reserviors, is then sampled detection, if fluorinion concentration be less than etc.
In 10mg/L, then qualified discharge or the follow-up denitrification system of entrance continue with；Regulating reservoir is back to if not up to standard；
J) level-one fluorine sedimentation basin and two level fluorine sedimentation basin pond base sludge are periodically discharged into fluorine sludge concentration tank, and throw through pump
PAM is added to promote flocks, filter-press dehydration is then carried out by plate and frame filter press, obtains calcium fluoride sludge；Pressing filtering liquid and fluorine sludge are dense
The supernatant in contracting pond is discharged into two level fluorine reaction tank, and the reaction was continued；
K) calcium fluoride sludge that the solid content that press filtration obtains is 50%, which is put into drying oven, dries, and drying temperature control exists
150~250 DEG C, drying materials time control makes sludge thoroughly dry, it is ensured that moisture percentage in sewage sludge is less than in 30min~60min
5%.
L) calcium fluoride sludge and lime, coke mix after drying into calcium fluoride containing 7%~10%, limy 50%~
80%th, the mixture containing coke 5%~10%, is made the iron melt desulfurizing agent for blast furnace steel-making.
It advanced optimizes, liquid caustic soda described in step a) is sodium hydroxide solution of the content 30%.
It advanced optimizes, using PVDF/PTFE organic films in ultra micro seperator described in step b), membrane aperture 10~
200nm, 5~10bar of operating pressure, 30~50HZ of vibration frequency, Oscillation Amplitude 10-20mm.
The beneficial effects of the present invention are：
(1) separation of solid and liquid is carried out to the waste water after neutralization using ultra micro seperator, qualified water outlet is directly made, and make sludge
It is concentrated, PAC, PAM, the heavy metal that saving traditional depositing technology need to add track down and arrest the medicaments such as agent, and the present invention uses ultra micro
Seperator carries out separation of solid and liquid, does not need to add these medicaments herein, is only added during follow-up sludge dewatering a small amount of
PAM；Dosage saves the medicament expense very much, saved in day-to-day operation；By the way that different films is selected to produce water water
It is of fine quality in traditional precipitation+sand filtration technique.
(2) it by all adding liquid caustic soda come heavy-metal ion removal, is allowed to be converted into metal hydroxides sludge so that dirty
Mud ingredient is controlled, and metal ion content is greatly improved, with recovery value.
(3) it is dried by medium temperature, makes metal hydroxides drying sludge and partially dehydrated decomposition so that metal hydroxides
Metal in sludge ion concentration further improves, and the content of nickel can reach high-grade lateritic nickel ore in the metal mud after drying
Nickel content is allowed to the grade requirement for meeting blast furnace process nickel-iron alloy raw material, and has the possibility for melting down smelting stainless steel.
(4) calcium chloride is added by producing water to ultra micro seperator to make a return journey Natural zeolite, be allowed to be converted into calcium fluoride sludge, make
Detached with metal hydroxides sludge, purity is greatly improved, with recovery value.
(5) dried by medium temperature, calcium fluoride sludge made to survey bottom drying, and with other raw material proportionings, be allowed to meet steel-making de-
Sulphur requirement can be used as iron melt desulfurizing agent to be used for blast furnace steel-making.
(6) mixture that the sludge that conventional lime technique generates is metal hydroxides, calcirm-fluoride and lime residue are formed,
Complicated component can not recycle, and can only be used as dangerous solidification disposal of waste, and cost of disposal is high, and environment hidden danger is big.It adopts new technology
Afterwards, the separation of simple metal hydroxide sludge and pure calcium fluoride sludge is realized, is allowed to had the value recycled, realizes
The zero-emission of dangerous solid waste has great economic value and environmental value.
Description of the drawings
Fig. 1 is the process flow chart of the present invention.
Specific embodiment
The present invention is described in further detail for specific embodiment below in conjunction with the accompanying drawings.
As shown in Figure 1, the method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes, specifically includes following steps：
A) the nitration mixture waste water that metal industry pickling generates is discharged into regulating reservoir, is then promoted in neutralization chamber through pump, in
Divide two-stage with slot, every grade adds in content and adjusts PH in 30% sodium hydroxide solution, and wherein level-one neutralization chamber PH controls exist：5-
6；Two level neutralization chamber PH controls exist：7.5-8.5；The neutralization reaction of a large amount of metal ions needs certain reaction time, divides two-stage
It is controlled convenient for PH, pH value that wherein sodium hydroxide solution controls as needed is determined, it is only necessary to be adjusted to the pH value of setting；
B) waste water after neutralizing is introduced into heavy metal sewage sludge circulatory pool, carries out preliminary separation of solid and liquid；
C) the top turbid of solid-liquid separation is promoted into introducing ultra micro seperator through pump and is filtered concentration, the clear liquid filtered out
Ultra micro discharge bay is discharged into, the dope filtered out is flowed back into heavy metal sewage sludge circulatory pool, continues to detach；
D) heavy metal sewage sludge circulatory pool base sludge is periodically discharged into sludge concentration tank through pump, and is added PAM and promoted flocks,
Then filter-press dehydration is carried out by plate and frame filter press, obtains the metal hydroxides sludge that moisture content is 50%；
E) the metal hydroxides sludge that the moisture content that press filtration obtains is 50% enters drying oven and is dried, drying temperature
Control makes sludge thoroughly dry, and make part hydroxide kinetics into oxide, drying materials time at 150~200 DEG C
Control is between 30min~60min；
F) the metal mud obtained after drying and the raw material mix dispensing used in smelting stainless steel, reach into after stove requirement, into
Blast furnace or the direct smelting stainless steel of electric furnace；The content of nickel can reach the nickel content of high-grade lateritic nickel ore in the metal mud；
G) waste water in ultra micro discharge bay is promoted through pump into level-one fluorine reaction tank, and level-one fluorine reaction tank is divided to two lattice, respectively
Carry out reaction fluorine removal by adding calcium chloride, water outlet enters level-one fluorine sedimentation basin and carries out mud-water separation, the supernatant isolated into
Enter level-one fluorine clear water reserviors；Wherein, chlorination in level-one fluorine reaction tank is controlled according to the fluorinion concentration of level-one fluorine sedimentation basin water outlet
The dosage of calcium, water outlet fluorinion concentration control is within 20mg/L；
H) level-one fluorine clear water water is promoted through pump into two level fluorine reaction tank, and two level fluorine reaction tank is divided to two lattice, passes through respectively
It adds calcium chloride, PAC (aluminium polychloride) and PAM (polyacrylamide) and carries out reaction fluorine removal, water outlet enters two level fluorine sedimentation basin
Carry out mud-water separation；Wherein, according to two level fluorine sedimentation basin be discharged fluorinion concentration come control calcium chloride in two level fluorine reaction tank,
The dosage of PAC and PAM, water outlet fluorinion concentration control is within 10mg/L；
I) supernatant isolated enters two level fluorine clear water reserviors, is then sampled detection, if fluorinion concentration be less than etc.
In 10mg/L, then qualified discharge or the follow-up denitrification system of entrance continue with；Regulating reservoir is back to if not up to standard；
J) sludge of level-one fluorine sedimentation basin and two level fluorine sedimentation basin bottom precipitation is periodically discharged into fluorine sludge concentration tank through pump,
And add PAM and promote flocks, filter-press dehydration is then carried out by plate and frame filter press, the calcirm-fluoride for obtaining moisture content about 50% is dirty
Mud；The supernatant of pressing filtering liquid and fluorine sludge concentration tank is discharged into two level fluorine reaction tank, and the reaction was continued；
K) calcium fluoride sludge that the solid content that press filtration obtains is 50%, which is put into drying oven, dries, and drying temperature control exists
150~250 DEG C, sludge is made thoroughly to dry, it is ensured that moisture percentage in sewage sludge be less than 5%, drying materials time control 30min~
60min；
L) calcium fluoride sludge and lime, coke mix after drying into calcium fluoride containing 7%~10%, limy 50%~
80%th, the mixture containing coke 5%~10%, is made the iron melt desulfurizing agent for blast furnace steel-making.
Embodiment 1
Method using the present invention handles the pickling nitration mixture waste water that certain cold rolling workshop section of Stainless Steel Plant is discharged, and concrete operations are such as
Under：
First, the pickling nitration mixture waste water that cold rolling workshop section is discharged by certain Stainless Steel Plant introduces regulating reservoir, measures total in waste water
Iron 3000mg/L, chromium ion concentration 300mg/L, nickel ion concentration 90mg/L, fluorinion concentration 1400mg/L, PH 1~2 it
Between；
Pickling nitration mixture waste water is promoted to through pump in neutralization chamber by regulating reservoir again, neutralization chamber divides two-stage, and every grade adds in liquid
Alkali adjusts PH, and wherein level-one neutralization chamber PH control points are：5--6；Two level neutralization chamber PH control points are：7.5-8.5；
Then, the waste water after neutralization is introduced into sludge circulation pond, carries out preliminary separation of solid and liquid, and top turbid utilizes ultra micro point
It disembarks and is filtered concentration, the clear liquid filtered out is discharged into ultra micro discharge bay；The dope filtered out is returned in sludge circulation pond, is continued point
From；Ultra micro seperator uses PVDF organic films, membrane aperture 200nm, membrane flux 200L/ (m2.h)；Operating pressure 5-10bar, shakes
Dynamic frequency 30-50HZ, Oscillation Amplitude 15mm；Total iron mean concentration 1.5mg/L in clear liquid is measured after ultramicro separator separation, always
Lattice mean concentration 0.01mg/L, total nickel mean concentration 0.08mg/L, turbidity mean concentration is 0.01NTU.
Sludge circulation pond base sludge is periodically discharged into sludge concentration tank through pump, and is added PAM and promoted flocks, is then passed through
Plate and frame filter press carries out filter-press dehydration, obtains the metal hydroxides sludge of moisture content about 50%；Pressing filtering liquid and sludge circulation pond
Supernatant be discharged into sludge circulation pond.
The metal hydroxides sludge of the moisture content that press filtration obtains about 50%, which enters dryer, is dried, drying temperature control
System makes sludge thoroughly dry at 150~200 DEG C, and makes part hydroxide kinetics into oxide, the control of drying materials time
System is between 30min~60min；
The material component obtained after drying is：
The raw material in mass ratio 1 of metal mud and smelting stainless steel after drying:5 mix dispensings and ball processed, reaching will into stove
After asking, into blast furnace (or electric furnace) directly smelting ferronickel evanohm.
《Baosteel Desheng Stainless Steel Co., Ltd.'s Purchase specification-lateritic nickel ore》(CJ/BGDS02001-2016) in
Technical requirement：
It can be seen that the material after drying only needs to carry out necessary dispensing mix can to meet《It is limited that Baosteel moral contains stainless steel
Company's Purchase specification-lateritic nickel ore》(CJ/BGDS02001-2016) technical requirement in.
Traditional depositing technology is for in liquid caustic soda and for Process for Effluent, poor effect, general PAC dosages are in 30-
50mg/L；PAM dosages are in 2-3mg/L；Heavy metal tracks down and arrests the added amount of chemical such as agent in 1-2mg/L；And dosing final settling tanks goes out
Water still has the phenomenon that turbidity is exceeded, and the waste water after neutralization is carried out due to the use of ultra micro seperator in practical operation in the present invention
Separation of solid and liquid is directly made qualified water outlet, and is concentrated sludge, save PAC, PAM that traditional depositing technology need to add,
Heavy metal tracks down and arrests the medicaments such as agent, the medicament expense in day-to-day operation is saved, by selecting different film producing water water qualities excellent
In traditional precipitation+sand filtration technique.
Ultra micro discharge bay waste water is promoted through pump into level-one fluorine reaction tank, and level-one fluorine reaction tank is divided to two lattice, passes through throwing respectively
Calcium chloride is added to carry out reaction fluorine removal, water outlet enters level-one fluorine sedimentation basin and carries out mud-water separation.Supernatant enters level-one fluorine clear water reserviors.
The dosage of calcium chloride in level-one fluorine reaction tank is controlled according to the fluorinion concentration of level-one fluorine sedimentation basin water outlet, is discharged fluorine ion
Concentration is controlled within 20mg/L.
Level-one fluorine clear water water is promoted through pump into two level fluorine reaction tank, and two level fluorine reaction tank is divided to two lattice, passes through throwing respectively
Calcium chloride, PAC and PAM is added to carry out reaction fluorine removal, water outlet enters two level fluorine sedimentation basin and carries out mud-water separation.Supernatant enters two level
Fluorine clear water reserviors；Subsequently into detect tank, if fluorinion concentration within 10mg/L, qualified discharge or enters follow-up denitrogenation system
System continues with.Regulating reservoir is back to if not up to standard.Two are controlled according to the fluorinion concentration of two level fluorine sedimentation basin water outlet
The dosage of calcium chloride and PAC in grade fluorine reaction tank, water outlet fluorinion concentration control is within 10mg/L.
Level-one fluorine sedimentation basin and two level fluorine sedimentation basin pond base sludge are periodically discharged into fluorine sludge concentration tank, and add through pump
PAM promotes flocks, then carries out filter-press dehydration by plate and frame filter press, obtains the calcium fluoride sludge of moisture content about 50%.Press filtration
The supernatant of liquid and fluorine sludge concentration tank is discharged into two level fluorine reaction tank.
The calcium fluoride sludge of solid content 50% or so that press filtration obtains, which is put into drying oven, dries, and drying temperature control exists
150~250 DEG C, sludge is made thoroughly to dry, it is ensured that moisture percentage in sewage sludge be less than 5%, drying materials time control 30min~
Between 60min.
The material component obtained after drying is：
Typical steelmaking ingredient component requirements
1st, molten iron pre-desulfurization agent component list：
It can be seen that：If you need to make molten iron pre-desulfurization agent, it is only necessary to carry out drying and mix corresponding calcium oxide, coke i.e.
It can.
2nd, steelmaking slag agent：
Steelmaking slag agent can also be made in calcirm-fluoride mud it can be seen from upper table ingredient, it is only necessary to be suitably modified and dispensing
.
After drying calcium fluoride sludge (in the calcium fluoride sludge after drying main component be calcirm-fluoride, content 99% with
On, pure calcirm-fluoride can be defaulted as and carry out dispensing) with unclassified stores (lime, coke etc.) match mix into calcium fluoride containing 4%~
10%th, molten iron pre-desulfurization agent or slag former is made for height in limy 50%~70%, the mixture containing coke 5%~10%
Stove is made steel.
The above is only the preferred implementation method of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as the present invention's
Protection domain.
Claims (5)
1. the method that the nitration mixture Sewage treatment that a kind of pickling of metal generates utilizes, which is characterized in that include the following steps：
a）The nitration mixture waste water that metal industry pickling generates is discharged into regulating reservoir, is then promoted in neutralization chamber through pump, neutralization chamber
Divide two-stage, every grade adds in liquid caustic soda and adjusts PH, and wherein level-one neutralization chamber PH controls exist：5-6；Two level neutralization chamber PH controls exist：
7.5-8.5；
b）Waste water after neutralization is introduced into heavy metal sewage sludge circulatory pool, carries out preliminary separation of solid and liquid；
c）The top turbid of solid-liquid separation is promoted into introducing ultra micro seperator through pump and is filtered concentration, the clear liquid filtered out is discharged into
Ultra micro discharge bay, the dope filtered out are flowed back into heavy metal sewage sludge circulatory pool, continue to detach；
d）Heavy metal sewage sludge circulatory pool base sludge is periodically discharged into through pump in heavy metal-polluted mud thickener, and is added PAM and promoted to coagulate
Then wadding carries out filter-press dehydration by plate and frame filter press, obtains metal hydroxides sludge；Again by pressing filtering liquid and sludge concentration tank
In supernatant reflux be discharged into sludge circulation pond；
e）Metal hydroxides sludge, which enters drying oven, is dried, and drying temperature control is at 150 ~ 200 DEG C, the drying materials time
It controls in 30min ~ 60min, obtains metal mud；
f）The metal mud obtained after drying and the raw material mix dispensing used in smelting stainless steel, reach into after stove requirement, into blast furnace
Or the direct smelting stainless steel of electric furnace；
g）Waste water in ultra micro discharge bay is promoted through pump into level-one fluorine reaction tank, and level-one fluorine reaction tank is divided to two lattice, passes through respectively
It adds calcium chloride and carries out reaction fluorine removal, water outlet enters level-one fluorine sedimentation basin and carries out mud-water separation, and the supernatant isolated enters one
Grade fluorine clear water reserviors；
h）Waste water in level-one fluorine clear water reserviors is promoted through pump into two level fluorine reaction tank, and two level fluorine reaction tank is divided to two lattice, leads to respectively
It crosses and adds calcium chloride, PAC and PAM and carry out reaction fluorine removal, water outlet enters two level fluorine sedimentation basin and carries out mud-water separation；
i）The supernatant isolated enters two level fluorine clear water reserviors, is then sampled detection, if fluorinion concentration is less than or equal to
10mg/L, then qualified discharge or the follow-up denitrification system of entrance continue with；Regulating reservoir is back to if not up to standard；
j）The sludge of level-one fluorine sedimentation basin and two level fluorine sedimentation basin bottom precipitation is periodically discharged into fluorine sludge concentration tank, and throw through pump
PAM is added to promote flocks, filter-press dehydration is then carried out by plate and frame filter press, obtains calcium fluoride sludge, pressing filtering liquid and fluorine sludge are dense
The supernatant in contracting pond is discharged into ultra micro discharge bay, and the reaction was continued；
k）Calcium fluoride sludge is put into drying oven and dries, and drying temperature is controlled at 150 ~ 250 DEG C, and drying materials time control exists
30min~60min；
l）Calcium fluoride sludge after drying is with lime, coke mix into calcium fluoride containing 4% ~ 10%, limy 50% ~ 70%, containing coke
The iron melt desulfurizing agent for blast furnace steel-making is made in 5% ~ 10% mixture.
2. the method that the nitration mixture Sewage treatment that pickling of metal according to claim 1 generates utilizes, which is characterized in that step
a）Described in liquid caustic soda be sodium hydroxide solution of the content 30%.
3. the method that the nitration mixture Sewage treatment that pickling of metal according to claim 1 generates utilizes, which is characterized in that step
b）Described in ultra micro seperator using PVDF/PTFE organic films, 10 ~ 200nm of membrane aperture, 5 ~ 10bar of operating pressure, vibration frequency
30 ~ 50HZ of rate, Oscillation Amplitude 10-20mm.
4. the method that the nitration mixture Sewage treatment that pickling of metal according to claim 1 generates utilizes, which is characterized in that step
g）The middle fluorinion concentration being discharged according to level-one fluorine sedimentation basin controls the dosage of calcium chloride in level-one fluorine reaction tank, is discharged fluorine
Ion concentration is controlled in≤20mg/L.
5. the method that the nitration mixture Sewage treatment that pickling of metal according to claim 1 generates utilizes, which is characterized in that step
h）The middle fluorinion concentration being discharged according to two level fluorine sedimentation basin controls adding for calcium chloride in two level fluorine reaction tank, PAC and PAM
Amount, water outlet fluorinion concentration control is in≤10mg/L.
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