Background technology
During Steel further processing, acid pickling and rust removing processing need to be carried out to its surface.Conventional pickle is hydrochloric acid and sulphur
Acid, at present most enterprises using hydrochloric acid as pickle.Steel can produce substantial amounts of pickle liquor after chlorohydric acid pickling.
The composition of hydrochloric acid pickling waste liquor is mainly hydrogen chloride, frerrous chloride, water and a small amount of impurity, and each component content is with acid cleaning process, behaviour
Make that temperature, rolling shapes and specification be different and different, general chloride containing ferrous iron 10~20%, hydrogen chloride 3~10%.Wherein, steel
Pickle liquor caused by hot rolling typically contains 1~5g/L H+, 60~250g/L Fe2+, because pickle liquor has seriously
Corrosivity, be put into《National Hazard waste register》, such waste liquid, which directly discharges, not only seriously pollutes environment, and causes
Greatly waste.
Can not directly it be discharged by national requirements for environmental protection pickle liquor, traditional processing method has neutralisation, evaporation knot
Crystallization or roasting recovery hydrochloric acid method.The shortcomings that neutralisation is the method that current iron and steel enterprise generally uses, but it is present is also relatively prominent
Go out, on the one hand to consume substantial amounts of basic agent (such as caustic soda, lime), processing cost is sufficiently expensive;On the other hand can give birth to again
Into the iron containing sludge for being largely difficult to dispose, covert secondary pollution is caused to environment;Evaporative crystallization method is by being heated to acid pickle
Watery hydrochloric acid is formed after evaporation, condenser condensation, workshop is returned to and reuses;By being concentrated by evaporation, cooling concentration liquation goes out FeCl2
Crystallization, obtains solid product.The advantages of technology is to handle acid pickle, and the hydrochloric acid of recovery more than 98%, concentration of hydrochloric acid is than useless
Liquid concentration declines 1%~4%;Make Fe2+All with FeCl2Solid form is discharged, and equipment is simple, and investment is small, and processing cost is low;
But this technology, there is great environmental risk and the market risk, in order to cost-effective, the hydrochloric acid for pickling uses it more
The by-product hydrochloric acid of his chemical industry, wherein containing the even poisonous material of substantial amounts of organic matter, although to steel industry pickling
Do not influence, but the product such as frerrous chloride obtained after being concentrated by evaporation is inevitably even poisonous containing some organic matters
Material, and FeCl2Usually used as water purification agent, must once the product such as above-mentioned poisonous frerrous chloride is used in water process
So cause secondary pollution to handled water, consequence is hardly imaginable.In addition water purification agent market demand is limited, also seriously limits
The application of the technology.Roasting recovery hydrochloric acid method is by the heating of waste liquid, dehydration, the oxidation of ferrous salt and hydrolysis, hydrogen chloride gas
Collect and absorption hydrochloric acid is organically incorporated in a system and completed in the lump, with disposal ability is big, facility is compact, resource is returned
High income (up to 98%~99%), regeneration acid concentration is high, contains Fe in acid2+Less, aoxidize Iron grade high (up to more than 98%) and
Using it is wide the features such as, therefore obtained Rapid Popularization;At present, the country has over two hundred set roasting method to reclaim hydrochloric acid subtraction unit continuous
Operation.The existing roasting most commonly used technology of recovery hydrochloric acid method is the Ruthner technologies of Austria, and the country uses mostly
This technology.But as requirement of the steel industry to pickling efficiency is more and more high, pickling medium is used as using the hydrochloric acid of high concentration
Turn into trend to increase substantially pickling efficiency.But hydrochloric acid is in the case of normal pressure, 22% is its azeotropic concentration, Ruthner works
Skill technology due to using water absorb HCl technique, its regenerate hydrochloric acid concentration can not exceed 22%wt, can only achieve 18%-~
20%wt, can not meet the needs of enterprise regenerates hydrochloric acid to 22% concentrations above.
Embodiment
Specific embodiment of the present utility model is described further below in conjunction with the accompanying drawings:
As shown in figure 1, a kind of highly concentrated pickle liquor regenerative system described in the utility model, including hydrolysis calcining furnace 1, two level
Dust arrester, preconcentrator 5, B grade condensing unit, air cooling tower 10, hydrochloric acid absorption tower 12 and scrubbing tower 16;The hydrolysis calcining
The top exhanst gas outlet of stove 1 pass sequentially through by cyclone separator 2 connected with the two-stage dust removal device that multi-tube dust cleaner 3 forms it is pre- dense
The top smoke inlet of contracting device 5;The dust outlet of hydrolysis calcining furnace 1, cyclone separator 2 and multi-tube dust cleaner 3 connects strength respectively
Conveyance conduit, Pneumatic conveying pipeline are provided with Geldart-D particle blower fan 4;The bottom liquid outlet of preconcentrator 5 passes through circulation all the way
Concentrating pump 6 connects the overhead-liquid entrance of preconcentrator 5, and another way connects the overhead-liquid of hydrolysis calcining furnace 1 by feed pump 7
Spray gun;Concentration acid solution entrance connection high concentration pickle liquor conveyance conduit on preconcentrator 5;The gas vent of preconcentrator 5
Pass sequentially through and connect the bottom gas of hydrochloric acid absorption tower 12 with the B grade condensing unit that the second condenser 9 forms by the first condenser 8
Entrance;First condenser 8 connects the liquid inlet of mixed in hydrochloric acid groove 13 with the liquid outlet of the second condenser 9;First condenser 8
Pass through the outlet of the connection air cooling tower 10 of air cooling circulating pump 11, the entrance of air cooling circulating pump 11 with the cooling water inlet of the second condenser 9
Connection desalted water conveyance conduit in addition;First condenser 8 connects entering for air cooling tower 10 with the coolant outlet of the second condenser 9
Mouthful;The liquid inlet of the bottom liquid outlet of hydrochloric acid absorption tower 12 connection mixed in hydrochloric acid groove 13, the liquid outlet of mixed in hydrochloric acid groove 13
Hydrochloric acid product is connected by hydrochloric acid pump 14 and sends pipeline outside;The outlet of the top gas of hydrochloric acid absorption tower 12 is washed by the connection of acidproof blower fan 15
Wash the bottom gas inlet of tower 16;The bottom liquid outlet of scrubbing tower 16 connects the top liquid of hydrochloric acid absorption tower 12 by washing pump 27
Body entrance and the overhead-liquid entrance of scrubbing tower 16;The overhead-liquid entrance of scrubbing tower 16 connects desalted water conveyance conduit in addition.
As shown in Fig. 2 using a kind of highly concentrated pickle liquor of highly concentrated pickle liquor regenerative system described in the utility model again
Raw technique comprises the following steps:
1) Fe ion concentrations > 150g/L high concentration pickle liquor concentrates in preconcentrator 5 through high-temperature flue gas, concentration
Fe ion concentrations > 200g/L pickle liquor, which enters in hydrolysis roaster 1, afterwards carries out pyrolytic, decomposition temperature 400~700
℃;
2) high-temperature flue gas containing HCl prepared by step 1) is sequentially sent into cyclone dust collectors 2 to be removed with multi-tube dust cleaner 3
Dirt processing, wherein more than 95% dust recycles after being collected as iron oxide red;
3) step 2) is obtained into gas and is sent into preconcentrator 5, contacted with high concentration pickle liquor, complete dedusting, liquid
The processes such as body concentration, gas cooling, 85~95 DEG C of 5 operation temperature of preconcentrator;
4) B-grade condensation will be carried out through the gas after step 3) processing, condensation temperature is respectively 65~75 DEG C and 45~55
DEG C, obtain the high concentration that concentration is 23~25%wt and regenerate hydrochloric acid;
5) hydrochloric acid absorption tower 12 will be sent into through the gas after step 4) processing, be absorbed with water, it is 23~25% to obtain concentration
Wt high concentration regeneration hydrochloric acid;Flue gas after absorption HCl gases is sent to scrubbing tower 16 and washed, the row up to standard of the flue gas after washing
Put, cleaning solution uses as absorption by Hydrochloric Acid liquid.
350~450 DEG C of 1 top temperature top of the hydrolysis roaster, 650~750 DEG C of bottom temperature, gauge pressure -200~
300Pa。
A kind of highly concentrated pickle liquor regenerative system described in the utility model is improved in existing Ruthner technologies, high
The pickle liquor of concentration, which enters after being concentrated in preconcentrator 5 by high-temperature flue gas in hydrolysis calcining furnace 1, carries out pyrolytic, obtains
High-temperature flue gas by entering preconcentrator 5 after cyclone dust collectors 2 and the dedusting of multi-tube dust cleaner 3, with pickle liquor to be processed
Contacted, the gas that temperature is reduced to 85-95 DEG C is not directly to be absorbed with water, but enters B grade condensing unit 8,9
Condensed, the HCl in flue gas is got off with water condensation;Due to avoiding the addition of water, allow the HCl of high concentration and water same
When condense out, avoid the constant boiling point of hydrochloric acid solution, realize regeneration concentration of hydrochloric acid more than more than 22%.Cigarette after condensation process
Containing the HCl that concentration is higher in gas, absorbed in hydrochloric acid absorption tower 12 using the water necessarily matched, concentration needed for acquisition
Hydrochloric acid.The tail gas for absorbing hydrochloric acid further absorbs by scrubbing tower 16, tail gas qualified discharge.
Following examples are implemented under premised on technical solutions of the utility model, give detailed embodiment
With specific operating process, but the scope of protection of the utility model is not limited to following embodiments.Side used in following embodiments
Method is conventional method unless otherwise instructed.
【Embodiment 1】
1) hydrolysis calcining furnace 1 is preheated using natural gas as thermal source, is then heated to required temperature, wherein furnace roof
400 DEG C of temperature, 700 DEG C of bottom temperature;High concentration pickle liquor is added in preconcentrator 5, while to cooling high-temperature fume,
Realize the pre-concentration of high concentration pickle liquor.
The high concentration pickling component of effluent composition of required processing is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
47.91 |
105.402 |
Fe3+=16.51g/L |
FeCl2 |
340.45 |
748.99 |
Fe2+=150.0g/L |
HCl |
75.73 |
166.606 |
— |
H2O |
911.1 |
2004.42 |
— |
Amount to |
1375.19 |
3025.418 |
— |
Place need to manage 3.025 tons of pickle liquor per hour.
2) the pickle liquor composition composition after the pre-concentration of preconcentrator 5 is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
63.87 |
105.3855 |
Fe3+=22.01g/L |
FeCl2 |
453.96 |
749.034 |
Fe2+=200g/L |
HCl |
135.29 |
223.2285 |
— |
H2O |
683.32 |
1127.478 |
— |
Amount to |
1336.44 |
2205.126 |
— |
Gas componant composition after pyrohydrolysis is as shown in the table:
Composition |
Volume % |
HCl |
10.5 |
H2O |
39.8 |
O2 |
3.77 |
N2 |
42.16 |
CO2 |
3.77 |
Volume of gas is 9800m3, 400 DEG C of temperature.Contain Fe in gas2O360kg, after two-stage dust removal, dust
Yield is 57kg, and the rate of recovery reaches 95%.
Hydrolyze the furnace bottom of calcining furnace 1 and collect iron oxide red powder 450kg, wherein Fe2O3Content is 98.8%wt, Cl contents
1.01%wt, heap density 400kg/m3。
Gas componant composition after the concentration of preconcentrator 5:
Composition |
Volume % |
HCl |
7.88 |
H2O |
49.9 |
O2 |
3.18 |
N2 |
35.5 |
CO2 |
3.18 |
Volume of gas is 6413m3/ h, density 0.818kg/m3, 93.5 DEG C of temperature.
3) B-grade condensation, absorption, washing are carried out:
Wherein the condensation temperature of the first condenser 8 is 70 DEG C, and the condensation temperature of the second condenser 9 is 50 DEG C.
The liquid inlet volume of hydrochloric acid absorption tower 12 is 224.4kg/h, and wherein HCl contents are 2%wt.
The hydrochloric acid content obtained after B-grade condensation and absorption by Hydrochloric Acid is 2629kg/h, concentration 23%wt.
Gas componant after scrubbing tower 16, which forms, is:
Composition |
Volume % |
HCl |
1.0×10-3 |
H2O |
8.87 |
O2 |
6.95 |
N2 |
77.0 |
CO2 |
7.18 |
Volume of gas 2700m3/h, 41 DEG C of temperature.
【Embodiment 2】
1) hydrolysis calcining furnace 1 is preheated using natural gas as thermal source, is then heated to required temperature, wherein furnace roof
350 DEG C of temperature, 650 DEG C of bottom temperature;High concentration pickle liquor is added in preconcentrator 5, while to cooling high-temperature fume,
Realize the pre-concentration of high concentration pickle liquor;
Handled high concentration pickling component of effluent composition is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
47.91 |
105.402 |
Fe3+=16.51g/L |
FeCl2 |
340.45 |
748.99 |
Fe2+=150.0g/L |
HCl |
75.73 |
166.606 |
|
H2O |
911.1 |
2004.42 |
|
Amount to |
1375.19 |
3025.418 |
|
Face need to handle 3.025 tons of pickle liquor amount per hour
2) composition composition of the high concentration pickle liquor after the pre-concentration of preconcentrator 5 is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
61.10 |
105.7 |
Fe3+=21.21g/L |
FeCl2 |
435.28 |
753.0 |
Fe2+=191.9g/L |
HCl |
130.1 |
224.9 |
|
H2O |
703.52 |
1172.5 |
|
Amount to |
1330 |
2300 |
|
Liquid after concentration carries out pyrohydrolysis, and the gas componant composition after hydrolysis is as shown in the table:
Composition |
Volume % |
HCl |
10.5 |
H2O |
39.5 |
O2 |
3.95 |
N2 |
42.1 |
CO2 |
3.95 |
Volume of gas adds up to 8526m3/ h, 350 DEG C of temperature.
Contain Fe in gas2O345kg, dust yield are 43.2kg, and the rate of recovery reaches 96%.
Hydrolyze the furnace bottom of calcining furnace 1 and collect iron oxide red powder 452kg, wherein Fe2O3Content 98.2%wt, Cl content
1.51%wt, heap density 400kg/m3。
Gas componant composition after the concentration of preconcentrator 5 is as shown in the table:
Composition |
Volume % |
HCl |
7.83 |
H2O |
48.3 |
O2 |
3.58 |
N2 |
36.8 |
CO2 |
3.49 |
Volume of gas is 5761m3/ h, density 0.819kg/m3, 92.3 DEG C of temperature.
3) B-grade condensation, absorption, washing are carried out;
Wherein 70 DEG C of the condensation temperature of the first condenser 8,50 DEG C of the condensation temperature of the second condenser 9.
The liquid inlet volume of hydrochloric acid absorption tower 12 is 224.4kg/h, and wherein HCl contents are 2%wt.
The hydrochloric acid content obtained after B-grade condensation and absorption by Hydrochloric Acid is 2314kg/h, concentration 23%wt.
Gas componant composition after scrubbing tower 16 is as shown in the table:
Composition |
Volume % |
HCl |
1.0×10-3 |
H2O |
5.52 |
O2 |
8.85 |
N2 |
74.8 |
CO2 |
10.83 |
Gas volume 2537m3/ h, 42 DEG C of temperature.
【Embodiment 3】
1) hydrolysis calcining furnace 1 is preheated using natural gas as thermal source, is then heated to required temperature, wherein furnace roof
450 DEG C of temperature, 750 DEG C of bottom temperature;High concentration pickle liquor is added in preconcentrator 5, while to cooling high-temperature fume
Realize the pre-concentration of pickle liquor;
Handled high concentration pickling component of effluent composition is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
47.91 |
105.402 |
Fe3+=16.51g/L |
FeCl2 |
340.45 |
748.99 |
Fe2+=150.0g/L |
HCl |
75.73 |
166.606 |
|
H2O |
911.1 |
2004.42 |
|
Amount to |
1375.19 |
3025.418 |
|
Need to handle 3.025 tons of high concentration pickle liquor per hour.
2) composition composition of the high concentration pickle liquor after the pre-concentration of preconcentrator 5 is as shown in the table:
Composition |
Content g/L |
Flow Kg/h |
Remarks |
FeCl3 |
66.90 |
105.7 |
Fe3+=22.01g/L |
FeCl2 |
461.7 |
729.5 |
Fe2+=200g/L |
HCl |
132.1 |
208.7 |
|
H2O |
719.3 |
1136.1 |
|
Amount to |
1380 |
2180.0 |
|
Liquid carries out pyrohydrolysis after pre-concentration, and the gas componant composition after hydrolysis is as shown in the table:
Composition |
Volume % |
HCl |
10.4 |
H2O |
38.71 |
O2 |
4.33 |
N2 |
42.68 |
CO2 |
3.88 |
Volume of gas adds up to 10593m3, 450 DEG C of temperature.
Contain Fe in gas2O370kg, dust yield are 66.5kg, and the rate of recovery reaches 95%.
Hydrolyze the furnace bottom of calcining furnace 1 and collect iron oxide red powder 435kg, wherein Fe2O3Content 99.1%wt, Cl content
0.78%wt, heap density 400kg/m3。
Gas componant composition after preconcentrator is as shown in the table:
Composition |
Volume % |
HCl |
7.94 |
H2O |
50.41 |
O2 |
3.52 |
N2 |
34.95 |
CO2 |
3.18 |
Volume of gas is 6610m3/ h, density 0.818kg/m3, 93.9 DEG C of temperature
3) B-grade condensation, absorption, washing are carried out;
Wherein 70 DEG C of the condensation temperature of the first condenser 8,50 DEG C of the condensation temperature of the second condenser 9.
The liquid that enters of hydrochloric acid absorption tower 12 is 255kg/h, and wherein HCl contents are 2%wt.
By B-grade condensation, the hydrochloric acid content then obtained after absorption by Hydrochloric Acid is 2743kg/h, concentration 23%wt.
Gas after scrubbing tower 16, which forms, is:
Composition |
Volume % |
HCl |
1.0×10-3 |
H2O |
8.91 |
O2 |
7.69 |
N2 |
76.6 |
CO2 |
6.80 |
Gas volume 2767m3/ h, 42 DEG C of temperature.
It is described above, the only preferable embodiment of the utility model, but the scope of protection of the utility model is not
This is confined to, any one skilled in the art is in the technical scope that the utility model discloses, according to this practicality
New technical scheme and its utility model design are subject to equivalent substitution or change, should all cover in protection model of the present utility model
Within enclosing.