CN108640383A - A kind of technique and its system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation - Google Patents
A kind of technique and its system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation Download PDFInfo
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
A kind of technique and its system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation, acid ammonium salt vanadium wastewater is sent into level-one except in silicon tank, desiliconizing agent pulverized limestone is added, it carries out once removing silicon, it is separated by solid-liquid separation by filter press, two level is sent into except in silicon tank, desiliconizing agent calcium chloride is added, it carries out secondary except silicon, pass through micropore fine filtration solid-liquid separation, level-one is sent into except in chromium calcium tank, the concentrated sulfuric acid is added, adjust pH value, after the reaction of reducing agent sodium pyrosulfite is added, it is added and removes chromium calcium agent soda ash and sodium hydroxide, after deliming, it is separated by solid-liquid separation by filter press, it is sent into two level deliming tank, calcium remover sodium phosphate two level deliming is added, micropore fine filtration solid-liquid separation.Advantage is：Pass through the harmful ions such as selective removal silicon, calcium, so that the steam stripping ammonia-removing tower system operation period is improved 4 times, reach 150 days or more, reduces vapour maintenance cleaning up cost and production suspension induced losses, realize vanadic anhydride continuous production operational objective, it is ensured that vanadium wastewater deamination qualified discharge.
Description
Technical field
The invention belongs to Leaching of Vanadium from Vanadium slag field of waste water treatment, more particularly to a kind of raising vanadic anhydride steam stripping ammonia-removing tower fortune
The technique and its system in row period.
Background technology
Vanadium titano-magnetite is through blast furnace process at vanadium-bearing hot metal, and converter oxidation is blown, and vanadium obtains after enrichment into slag phase
Vanadium slag.Leaching of Vanadium from Vanadium slag process is that vanadium slag is roasted ripe material, and clinker obtains vanadium solution with water extraction, to vanadium solution be added sulfuric acid,
Ammonium sulfate, steam heating precipitation prepare ammonium poly-vanadate, and ammonium poly-vanadate is through melting furnace drying, calcining and decomposing, fusing, cooling and then makes
Take piece of Vanadium product.Since vanadium solution is during precipitation, excessive ammonium sulfate is added, vanadium is converted into ammonium poly-vanadate
Precipitation, ammonium poly-vanadate are separated by solid-liquid separation through filter press press filtration, and Cr VI, a large amount of ammonium roots, vanadium wastewater sexavalence are contained in vanadium wastewater
After chromium reducing agent detoxifies, after waste water containing ammonium root adjusts 12 or more pH value with sodium hydroxide, heated by steam stripping ammonia-removing tower steam
To boiling removal of ammonia and nitrogen, using sulfuric acid absorption ammonia producing ammonium sulfate byproduct liquid, ammonium sulfate liquid returns to precipitation process and is used for precipitation
Production, vanadium wastewater is after deamination, qualified discharge.
It is harmful containing silicon (0.3-0.9g/L), calcium (0.1-0.4g/L) etc. in vanadium wastewater due to entering steam stripping ammonia-removing tower
Foreign ion, during steam stripping heats deamination, the gradual fouling of deammoniation tower destroys vapor-liquid equilibrium in tower, and steam stripping ammonia-removing tower is continuous
The cycle of operation is general less than 10 days, and deamination Tower System is forced parking maintenance one week or more cleaning incrustation, seriously affects five oxidations two
Vanadium continuous production is run.Currently, high efficiency dirt dispersion agent mode is added into vanadium wastewater for domestic vanadium extraction enterprise generally use
Fouling time, steam stripping ammonia-removing tower system continuous operation period is delayed to increase, but this method is the disadvantage is that steam stripping ammonia-removing tower system is transported
The row period is shorter, and still less than 40 days, vanadic anhydride is unable to continuous production, and vanadium extraction enterprise stop production to overhaul steam stripping ammonia-removing tower is often
Bring huge economic losses and environmental protection pressure.
Invention content
The technical problem to be solved in the present invention is to provide a kind of works improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation
Skill and its system are made the steam stripping ammonia-removing tower system operation period improve 4 times, are reached by harmful ions such as selective removal silicon, calcium
By 150 days or more, steam stripping ammonia-removing tower system overhaul cleaning up cost and production suspension induced losses are reduced, realize vanadic anhydride continuous production fortune
Row target, it is ensured that vanadium wastewater deamination qualified discharge.
The technology of the present invention solution is：
A kind of technique improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, is as follows：
(1) valve a is opened, the acid ammonium salt vanadium wastewater that temperature is 50 DEG C~70 DEG C is sent into level-one and is removed in silicon tank, valve is closed
Door a, starts agitating paddle, and desiliconizing agent pulverized limestone is added, and reacts 20min~30min, and control ph 9.0~10.5 is once removed
Silicon, analysis detection level-one except silicon tank solution it is siliceous≤0.1g/L after, will be once separated by solid-liquid separation by filter press except silicon solution；
(2) valve b is opened, filter press filter liquor is sent into two level except in silicon tank, valve b is closed, starts agitating paddle, addition removes
Silicea calcium chloride, react 10~30min, carry out it is secondary remove silicon, analysis detection two level except silicon tank solution it is siliceous≤0.05g/L after,
By secondary except silicon solution passes through micropore fine filtration solid-liquid separation；
(3) valve c is opened, the filtrate that micropore fine filtration device is filtered is sent into level-one except in chromium calcium tank, valve c is closed, and starts
Agitating paddle opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank, after adjusting solution ph≤2.5, chromium calcium is removed to level-one
Reducing agent sodium pyrosulfite is added in tank, level-one removes the quality of chromium and sodium pyrosulfite mass ratio 3.1 in chromium calcium tank filtrate:1~
3.4:1,20min~30min is reacted, is added into tank and removes chromium calcium agent soda ash and sodium hydroxide, neutralize pH value 9.5~10.5, instead
10min~30min is answered, after a deliming, analysis detection level-one is except solution calcic≤0.06g/L in chromium calcium tank, by a deliming
Solution is separated by solid-liquid separation by filter press；
(4) valve e is opened, the filtrate of filter press filtering is sent into two level deliming tank, valve e is closed, starts agitating paddle, to two
Grade deliming tank in be added calcium remover sodium phosphate, react 10min~30min, analysis detection two level deliming tank in solution calcic≤
After 0.0005g/L, by solution after reaction by micropore fine filtration solid-liquid separation after, filtrate be vanadium wastewater containing ammonium root convey
To steam stripping ammonia-removing tower system removal of ammonia and nitrogen.
Further, the mesh of 100 mesh of desiliconizing agent lime Powder Particle Size described in step (1)~400, active CaO mass contents >=
40%.
Further, calcium amount is with silicon amount mass ratio in silicon liquid is once removed in desiliconizing agent calcium chloride described in step (2)
3.0:1~7.0:1.
Further, chromium calcium agent soda ash and sodium hydroxide, soda ash and sodium hydroxide mass ratio 0.6 are removed described in step (3):
1~3.0:1.
Further, phosphorus amount is with calcium amount mass ratio in a deliming liquid in calcium remover sodium phosphate described in step (4)
1.0:1~4.0:1.
Further, the mesh of 200 mesh of desiliconizing agent lime Powder Particle Size described in step (1)~350 removes silicon described in step (2)
Calcium amount is 3.5 with silicon amount mass ratio in silicon liquid is once removed in agent calcium chloride:1~6.0:1, step (3) is described to remove chromium calcium agent soda ash
With sodium hydroxide mass ratio 0.9:1~1.5:1, phosphorus amount and calcium in a deliming liquid in calcium remover sodium phosphate described in step (4)
It is 2.0 to measure mass ratio:1~3.5:1.
A kind of acid ammonium salt pretreatment system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation, there is level-one to remove silicon
Tank, two level are characterized in that except silicon tank, level-one are except chromium calcium tank, two level deliming tank：The level-one passes through except silicon tank liquid outlet
Pipeline with two level except silicon tank is connected, in level-one except silicon tank and two level except being equipped with filter pressing pump I, pressure on the pipeline between silicon tank successively
Filter I, the two level except silicon tank by pipeline with level-one except chromium calcium tank is connected, two level remove silicon tank and level-one remove chromium calcium tank it
Between pipeline on be equipped with infusion pump I, micropore fine filtration device I successively, the level-one passes through pipeline and two level deliming except chromium calcium tank
Tank is connected, and is removed in level-one and is equipped with filter pressing pump II, filter press II successively on the pipeline between chromium calcium tank and two level deliming tank, described
Two level deliming tank is connected by pipeline with micropore fine filtration device II, between two level deliming tank and micropore fine filtration device II
Pipeline be equipped with infusion pump II, the micropore fine filtration device II outlet is connected with steam stripping ammonia-removing tower system entry by pipeline
It is logical.
Further, the level-one is connected with sulfuric acid storage tank except the sulfuric acid entrance of chromium calcium tank by pipeline, and chromium is removed in level-one
Pipeline between calcium tank and sulfuric acid storage tank is equipped with sulfuric acid delivery pump.
The level-one is equipped with acid ammonium salt vanadium wastewater pipeline except the acid ammonium salt vanadium wastewater entrance of silicon tank, and level-one removes silicon
The acid ammonium salt vanadium wastewater inlet duct of tank is equipped with valve a.
The two level is equipped with valve b except the inlet duct of silicon tank, and the level-one removes silicon solution inlet except the secondary of chromium calcium tank
Pipeline is equipped with valve c, and the level-one is equipped with valve d, the inlet tube of the two level deliming tank except the sulfuric acid inlet duct of chromium calcium tank
Road is equipped with valve e.
Advantageous effect of the present invention：
(1) simple for process, device structure is reasonable, easy to operate；
Silicon is removed twice using except silicon tank, except silicon effect is good；Using the deliming twice of deliming tank, deliming effect is good, and precipitation is greatly reduced
The objectionable impurities ion concentration such as silicon, calcium in waste water.
(2) the steam stripping ammonia-removing tower system operation period by improving 4 times less than 40 days, reaches 150 days or more.
This technique and its system, removing silicon, calcium plasma are thorough, are not required to that high efficiency dirt dispersion agent is added into vanadium wastewater, make
The steam stripping ammonia-removing tower system operation period is substantially improved, and realizes the operation of vanadic anhydride continuous production, it is ensured that vanadium wastewater deamination reaches
Mark discharge.
(3) micropore fine filtration device is utilized, the suspended particulate substances such as silicon in solution, calcium, chromium are greatly reduced.
This technique and its system not only greatly improve the steam stripping ammonia-removing tower system operation period, but also efflux wastewater are greatly reduced
Suspended matter makes ss suspended solid≤10mg/L, allows vanadium industrial discharge standard (SS≤50mg/L) well below country.
Description of the drawings
Fig. 1 is the acid ammonium salt pretreatment system structure of the raising vanadic anhydride steam stripping ammonia-removing tower cycle of operation of the present invention
Schematic diagram.
In figure：1- level-ones remove silicon tank, 2- filter presses I, and 3- two levels remove silicon tank, 4- micropore fine filtrations device I, and 5- level-ones remove chromium
Calcium tank, 6- filter presses II, 7- two level deliming tanks, 8- micropore fine filtrations device II, 9- filter pressing pumps I, 10- infusion pumps I, 11- press filtrations
Pump II, 12- infusion pumps II, 13- sulfuric acid storage tanks, 14- sulfuric acid delivery pumps.
Specific implementation mode
Embodiment 1
As shown, the acid ammonium salt pretreatment system of the raising vanadic anhydride steam stripping ammonia-removing tower cycle of operation, has level-one
Except silicon tank 1, two level except silicon tank 3, level-one except chromium calcium tank 5, two level deliming tank 7, the level-one except 1 liquid outlet of silicon tank by pipeline with
Two level is connected except silicon tank 3, and the level-one is equipped with acid ammonium salt vanadium wastewater pipe except the acid ammonium salt vanadium wastewater entrance of silicon tank 1
Road, level-one are equipped with valve a except the acid ammonium salt vanadium wastewater inlet duct of silicon tank；Level-one except silicon tank 1 and two level except silicon tank 3 it
Between pipeline on be equipped with filter pressing pump I 9, filter press I 2 successively, the two level except silicon tank 3 by pipeline and level-one except 5 phase of chromium calcium tank
Connection, in two level except silicon tank 3 and level-one remove and be equipped with infusion pump I 10, micropore fine filtration device successively on the pipeline between chromium calcium tank 5
I 4, and in two level except the inlet duct of silicon tank 3 is equipped with valve b, the level-one passes through pipeline and two level deliming tank 7 except chromium calcium tank 5
It is connected, is removed in level-one and be equipped with filter pressing pump II 11, filter press II 6 successively on the pipeline between chromium calcium tank 5 and two level deliming tank 7,
The level-one is connected with sulfuric acid storage tank 13 except the sulfuric acid entrance of chromium calcium tank 5 by pipeline, and chromium calcium tank 5 and sulfuric acid storage tank are removed in level-one
Pipeline between 13 is equipped with sulfuric acid delivery pump 14；The level-one is secondary except silicon solution inlet pipeline is equipped with valve except chromium calcium tank 5
Door c, sulfuric acid inlet duct are equipped with valve d, and the two level deliming tank 7 is connected by pipeline with micropore fine filtration device II 8,
Pipeline between two level deliming tank 7 and micropore fine filtration device II 8 is equipped with infusion pump II 12, and in the entrance of two level deliming tank
Pipeline is equipped with valve e, and the outlet of micropore fine filtration device II 8 is connected with steam stripping ammonia-removing tower system entry by pipeline.
The acid ammonium salt pretreatment system operating process for improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation is as follows：This work
Before process system starts, each valve is closed；
(1) valve a is opened, temperature 50 C acid ammonium salt vanadium wastewater (silicon 0.6g/L, calcium 0.3g/L, Cr VI 1.2g/L) is sent
Enter level-one except in silicon tank 1, valve a is closed, start agitating paddle, pulverized limestone (100 mesh of granularity, active CaO content 40%), control is added
PH value 9.0 processed reacts 20min, carries out once removing silicon, and analysis detection level-one removes the silicon siliceous 0.1g/L of tank solution, starts filter pressing pump I
9, it will once remove silicon solution and be separated by solid-liquid separation by filter press I 2；
(2) valve b is opened, I 2 filter liquor of filter press filter press is sent into two level except in silicon tank 3, valve b is closed, starts stirring
Paddle, calcium chloride is added, and (calcium amount removes silicon amount mass ratio 3.0 in silicon liquid with primary in desiliconizing agent calcium chloride:1) 30min, is reacted, is carried out
Secondary to remove silicon, analysis detection two level starts infusion pump I 10, by secondary except silicon solution leads to except the siliceous 0.05g/L of solution in silicon tank 3
Cross the separation of solid and liquid of micropore fine filtration device I 4；
(3) valve c is opened, the filtrate that micropore fine filtration device I 4 is filtered is sent into level-one except in chromium calcium tank 5, closing valve c is opened
Dynamic agitating paddle, opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank 5, after adjusting solution ph 2.5, chromium calcium is removed to level-one
Sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.1 are added in tank 5:1,20min is reacted, soda ash+hydrogen-oxygen is added into tank 5
Change sodium (soda ash and sodium hydroxide mass ratio 0.6:1) pH value 9.5, is neutralized, 10min is reacted, after a deliming, analysis detection level-one
Except solution calcic 0.06g/L in chromium calcium tank 5, start filter pressing pump II 11, will once remove calcium solution and pass through II 6 solid-liquid of filter press point
From；
(4) valve e is opened, the filtrate that filter press II 6 is filtered is sent into two level deliming tank 7, and valve e is closed, and starts agitating paddle,
Sodium phosphate (phosphorus amount and calcium amount mass ratio 1.0 in deliming liquid in calcium remover sodium phosphate are added into two level deliming tank 7:1), instead
10min, analysis is answered to detect solution calcic 0.0005g/L in two level deliming tank 7, solution after reaction is passed through micropore fine filtration device
After II 8 are separated by solid-liquid separation, filtrate is that vanadium wastewater containing ammonium root is delivered to steam stripping ammonia-removing tower system removal of ammonia and nitrogen, waste water NH after deamination3-
N2.5mg/L, ss suspended solid 8.5mg/L.
Embodiment 2
The acid ammonium salt pretreatment system of the vanadic anhydride steam stripping ammonia-removing tower cycle of operation is improved with embodiment 1.
It is as follows that vanadic anhydride steam stripping ammonia-removing tower improves cycle of operation process system operating process：This process system starts
Before, each valve is closed；
(1) valve a is opened, temperature 70 C acid ammonium salt vanadium wastewater (silicon 0.7g/L, calcium 0.4g/L, Cr VI 1.3g/L) is sent
Enter level-one except in silicon tank 1, valve a is closed, start agitating paddle, desiliconizing agent pulverized limestone (400 mesh of granularity, active CaO content is added
64%) 30min is reacted in, control ph 10.5, carries out once removing silicon, and analysis detection level-one removes the silicon siliceous 0.06g/L of tank solution,
Start filter pressing pump I 9, will once remove silicon solution and be separated by solid-liquid separation by filter press I 2；
(2) valve b is opened, I 2 filter liquor of filter press filter press is sent into two level except in silicon tank 3, valve b is closed, starts stirring
Paddle, calcium chloride is added, and (calcium amount removes silicon amount mass ratio 7.0 in silicon liquid with primary in desiliconizing agent calcium chloride:1) 10min, is reacted, is carried out
Secondary to remove silicon, analysis detection two level starts infusion pump I 10, by secondary except silicon solution leads to except the siliceous 0.01g/L of solution in silicon tank 3
Cross the separation of solid and liquid of micropore fine filtration device I 4；
(3) valve c is opened, the filtrate that micropore fine filtration device I 4 is filtered is sent into level-one except in chromium calcium tank 5, closing valve c is opened
Dynamic agitating paddle, opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank 5, after adjusting solution ph 1.8, chromium calcium is removed to level-one
Sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.4 are added in tank 5, reacts 30min, is added into tank 5 and removes chromium calcium agent soda ash
+ sodium hydroxide (soda ash and sodium hydroxide mass ratio 3.0:1) pH value 10.5, is neutralized, 30min is reacted, after a deliming, analysis inspection
Level-one is surveyed except solution calcic 0.05g/L in chromium calcium tank 5, starts filter pressing pump II 11, will once be consolidated by filter press II 6 except calcium solution
Liquid detaches；
(4) valve e is opened, the filtrate that filter press II 6 is filtered is sent into two level deliming tank 7, and valve e is closed, and starts agitating paddle,
Sodium phosphate (phosphorus amount and calcium amount mass ratio 4.0 in deliming liquid in calcium remover sodium phosphate are added into two level deliming tank 7:1), instead
30min, analysis is answered to detect solution calcic 0.0001g/L in two level deliming tank 7, solution after reaction is passed through micropore fine filtration device
After II 8 are separated by solid-liquid separation, filtrate is that vanadium wastewater containing ammonium root is delivered to steam stripping ammonia-removing tower system removal of ammonia and nitrogen, waste water NH after deamination3-
N 2.9mg/L, ss suspended solid 6.4mg/L.
Embodiment 3
The acid ammonium salt pretreatment system of the vanadic anhydride steam stripping ammonia-removing tower cycle of operation is improved with embodiment 1.
It is as follows that vanadic anhydride steam stripping ammonia-removing tower improves cycle of operation process system operating process：This process system starts
Before, each valve is closed；
(1) valve a is opened, temperature 60 C acid ammonium salt vanadium wastewater (silicon 0.3g/L, calcium 0.1g/L, Cr VI 1.6g/L) is sent
Enter level-one except in silicon tank 1, valve a is closed, start agitating paddle, pulverized limestone (350 mesh of granularity, active CaO content 76%), control is added
PH value 9.8 processed reacts 25min, carries out once removing silicon, and analysis detection level-one removes the silicon siliceous 0.06g/L of tank solution, starts filter pressing pump
I 9, it will once remove silicon solution and be separated by solid-liquid separation by filter press I 2；
(2) valve b is opened, I 2 filter liquor of filter press filter press is sent into two level except in silicon tank 3, valve b is closed, starts stirring
Paddle, calcium chloride is added, and (calcium amount removes silicon amount mass ratio 6.0 in silicon liquid with primary in desiliconizing agent calcium chloride:1) 25min, is reacted, is carried out
Secondary to remove silicon, analysis detection two level starts infusion pump I 10, by secondary except silicon solution leads to except the siliceous 0.009g/L of solution in silicon tank 3
Cross the separation of solid and liquid of micropore fine filtration device I 4；
(3) valve c is opened, the filtrate that micropore fine filtration device I 4 is filtered is sent into level-one except in chromium calcium tank 5, closing valve c is opened
Dynamic agitating paddle, opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank 5, after adjusting solution ph 1.5, chromium calcium is removed to level-one
Sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.2 are added in tank 5:1,26min is reacted, is added into tank 5 except chromium calcium agent is pure
Alkali+sodium hydroxide (soda ash and sodium hydroxide mass ratio 1.5:1) pH value 10.0, is neutralized, 25min is reacted, after a deliming, analysis
Level-one is detected except solution calcic 0.02g/L in chromium calcium tank 5, starts filter pressing pump II 11, once will pass through filter press II 6 except calcium solution
It is separated by solid-liquid separation；
(4) valve e is opened, the filtrate that filter press II 6 is filtered is sent into two level deliming tank 7, and valve e is closed, and starts agitating paddle,
Sodium phosphate (phosphorus amount and calcium amount mass ratio 3.5 in deliming liquid in calcium remover sodium phosphate are added into two level deliming tank 7:1), instead
20min, analysis is answered to detect solution calcic 0.0001g/L in two level deliming tank 7, solution after reaction is passed through micropore fine filtration device
After II 8 are separated by solid-liquid separation, filtrate is that vanadium wastewater containing ammonium root is delivered to steam stripping ammonia-removing tower system removal of ammonia and nitrogen, waste water NH after deamination3-
N 6.5mg/L, ss suspended solid 5.7mg/L.
Embodiment 4
The acid ammonium salt pretreatment system of the vanadic anhydride steam stripping ammonia-removing tower cycle of operation is improved with embodiment 1.
It is as follows that vanadic anhydride steam stripping ammonia-removing tower improves cycle of operation process system operating process：This process system starts
Before, each valve is closed；
(1) valve a is opened, 55 DEG C of acid ammonium salt vanadium wastewaters of temperature (silicon 0.5g/L, calcium 0.2g/L, Cr VI 1.5g/L) are sent
Enter level-one except in silicon tank 1, valve a is closed, start agitating paddle, pulverized limestone (200 mesh of granularity, active CaO content 81%), control is added
PH value 10.0 processed reacts 20min, carries out once removing silicon, and analysis detection level-one removes the silicon siliceous 0.07g/L of tank solution, starts press filtration
I 9 are pumped, silicon solution will be once removed and is separated by solid-liquid separation by filter press I 2；
(2) valve b is opened, I 2 filter liquor of filter press filter press is sent into two level except in silicon tank 3, valve b is closed, starts stirring
Paddle, calcium chloride is added, and (calcium amount removes silicon amount mass ratio 4.0 in silicon liquid with primary in desiliconizing agent calcium chloride:1) 20min, is reacted, is carried out
Secondary to remove silicon, analysis detection two level starts infusion pump I 10, by secondary except silicon solution leads to except the siliceous 0.006g/L of solution in silicon tank 3
Cross the separation of solid and liquid of micropore fine filtration device I 4；
(3) valve c is opened, the filtrate that micropore fine filtration device I 4 is filtered is sent into level-one except in chromium calcium tank 5, closing valve c is opened
Dynamic agitating paddle, opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank 5, after adjusting solution ph 2.0, chromium calcium is removed to level-one
Sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.3 are added in tank 5:1,24min is reacted, is added into tank 5 except chromium calcium agent is pure
Alkali+sodium hydroxide (soda ash and sodium hydroxide mass ratio 0.9:1) pH value 9.8, is neutralized, 20min is reacted, after a deliming, analysis
Level-one is detected except solution calcic 0.01g/L in chromium calcium tank 5, starts filter pressing pump II 11, once will pass through filter press II 6 except calcium solution
It is separated by solid-liquid separation；
(4) valve e is opened, the filtrate that filter press II 6 is filtered is sent into two level deliming tank 7, and valve e is closed, and starts agitating paddle,
Sodium phosphate (phosphorus amount and calcium amount mass ratio 2.0 in deliming liquid in calcium remover sodium phosphate are added into two level deliming tank 7:1), instead
18min, analysis is answered to detect solution calcic 0.0003g/L in two level deliming tank 7, solution after reaction is passed through micropore fine filtration device
After II 8 are separated by solid-liquid separation, filtrate is that vanadium wastewater containing ammonium root is delivered to steam stripping ammonia-removing tower system removal of ammonia and nitrogen, waste water NH after deamination3-
N 8.3mg/L, ss suspended solid 6.6mg/L.
Comparative example 1
55 DEG C of acid ammonium salt vanadium wastewaters of temperature (silicon 0.5g/L, calcium 0.3g/L, Cr VI 1.5g/L) are added and are removed in chromium tank, are added
After entering concentrated sulfuric acid adjusting solution ph 2.0, sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.2 is added, reacts 30min, to
In retort plus soda ash, neutralization pH value 9.2 react 30min, analyze detection solution calcic 0.26g/L, siliceous 0.44g/L, start
Solution is separated by solid-liquid separation by filter pressing pump by filter press, and filtrate is that vanadium wastewater containing ammonium root is delivered to the removing of steam stripping ammonia-removing tower system
Ammonia nitrogen, waste water NH after deamination3- N 16mg/L, ss suspended solid 48mg/L, 7.6 days steam stripping ammonia-removing tower system operation periods.
Comparative example 2
55 DEG C of acid ammonium salt vanadium wastewaters of temperature (silicon 0.3g/L, calcium 0.2g/L, Cr VI 1.3g/L) are added and are removed in chromium tank, are added
After entering concentrated sulfuric acid adjusting solution ph 1.8, sodium pyrosulfite, chromium and sodium pyrosulfite mass ratio 3.2 is added, reacts 30min, to
In retort plus soda ash, neutralization pH value 9.5 react 20min, analyze detection solution calcic 0.18g/L, siliceous 0.22g/L, Xiang Rong
High efficiency dirt dispersion agent is added in liquid, starts filter pressing pump, solution is separated by solid-liquid separation by filter press, filtrate is that precipitation containing ammonium root is useless
Water is delivered to steam stripping ammonia-removing tower system removal of ammonia and nitrogen, waste water NH after deamination3- N 13mg/L, ss suspended solid 160mg/L, stripping are de-
38.8 days ammonia Tower System cycles of operation.
1 acid ammonium salt vanadium wastewater of table is into index contrast table before steam stripping ammonia-removing tower
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Silicon, g/L | 0.05 | 0.01 | 0.009 | 0.006 | 0.44 | 0.22 |
| Calcium, g/L | 0.0005 | 0.0001 | 0.0001 | 0.0003 | 0.26 | 0.18 |
| Ss suspended solid, g/L | 8.5 | 6.4 | 5.7 | 6.6 | 48 | 160 |
2 acid ammonium salt vanadium wastewater steam stripping ammonia-removing tower system operation period of table contrast table
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| The cycle of operation | >=150 days | >=150 days | >=150 days | >=150 days | 7.6 it | 36.8 days |
It these are only specific embodiments of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of technique improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
It is as follows：
(1) valve a is opened, the acid ammonium salt vanadium wastewater that temperature is 50 DEG C~70 DEG C is sent into level-one and is removed in silicon tank, valve is closed
Door a, starts agitating paddle, and desiliconizing agent pulverized limestone is added, and reacts 20min~30min, and control ph 9.0~10.5 is once removed
Silicon, analysis detection level-one except silicon tank solution it is siliceous≤0.1g/L after, will be once separated by solid-liquid separation by filter press except silicon solution；
(2) valve b is opened, filter press filter liquor is sent into two level except in silicon tank, valve b is closed, starts agitating paddle, addition removes
Silicea calcium chloride, react 10min~30min, carry out it is secondary remove silicon, analysis detection two level except silicon tank solution it is siliceous≤0.05g/L
Afterwards, by secondary except silicon solution passes through micropore fine filtration solid-liquid separation；
(3) valve c is opened, the filtrate that micropore fine filtration device is filtered is sent into level-one except in chromium calcium tank, valve c is closed, and starts
Agitating paddle opens valve d, and to level-one except the concentrated sulfuric acid is added in chromium calcium tank, after adjusting solution ph≤2.5, chromium calcium is removed to level-one
Reducing agent sodium pyrosulfite is added in tank, level-one removes the quality of chromium and sodium pyrosulfite mass ratio 3.1 in chromium calcium tank filtrate:1~
3.4:1,20min~30min is reacted, is added into tank and removes chromium calcium agent soda ash and sodium hydroxide, neutralize pH value 9.5~10.5, instead
10min~30min is answered, after a deliming, analysis detection level-one is except solution calcic≤0.06g/L in chromium calcium tank, by a deliming
Solution is separated by solid-liquid separation by filter press；
(4) valve e is opened, the filtrate of filter press filtering is sent into two level deliming tank, valve e is closed, starts agitating paddle, to two
Grade deliming tank in be added calcium remover sodium phosphate, react 10min~30min, analysis detection two level deliming tank in solution calcic≤
After 0.0005g/L, by solution after reaction by micropore fine filtration solid-liquid separation after, filtrate be vanadium wastewater containing ammonium root convey
To steam stripping ammonia-removing tower system removal of ammonia and nitrogen.
2. the technique according to claim 1 for improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
The mesh of 100 mesh of desiliconizing agent lime Powder Particle Size described in step (1)~400, active CaO mass content >=40%.
3. the technique according to claim 1 for improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
Calcium amount is 3.0 with silicon amount mass ratio in silicon liquid is once removed in desiliconizing agent calcium chloride described in step (2):1~7.0:1.
4. the technique according to claim 1 for improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
Chromium calcium agent soda ash and sodium hydroxide, soda ash and sodium hydroxide mass ratio 0.6 are removed described in step (3):1~3.0:1.
5. the technique according to claim 1 for improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
Phosphorus amount and calcium amount mass ratio in a deliming liquid are 1.0 in calcium remover sodium phosphate described in step (4):1~4.0:1.
6. the technique according to claim 1 for improving the vanadic anhydride steam stripping ammonia-removing tower system operation period, it is characterized in that：
The mesh of 200 mesh of desiliconizing agent lime Powder Particle Size described in step (1)~350, calcium amount and one in desiliconizing agent calcium chloride described in step (2)
It is secondary except in silicon liquid silicon amount mass ratio be 3.5:1~6.0:1, step (3) is described to remove chromium calcium agent soda ash and sodium hydroxide mass ratio
0.9:1~1.5:1, phosphorus amount and calcium amount mass ratio in a deliming liquid are 2.0 in calcium remover sodium phosphate described in step (4):1~
3.5:1。
7. a kind of acid ammonium salt pretreatment system improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation, there is level-one to remove silicon
Tank, two level remove silicon tank, level-one except chromium calcium tank, two level deliming tank, it is characterized in that：The level-one except silicon tank liquid outlet by pipeline with
Two level is connected except silicon tank, in level-one except silicon tank and two level remove and be equipped with filter pressing pump I, filter press I successively on the pipeline between silicon tank,
The two level except silicon tank by pipeline with level-one except chromium calcium tank is connected, remove silicon tank and level-one in two level and remove pipe between chromium calcium tank
Infusion pump I, micropore fine filtration device I are equipped on road successively, the level-one is connected by pipeline with two level deliming tank except chromium calcium tank
It is logical, it is removed in level-one and is equipped with filter pressing pump II, filter press II successively on the pipeline between chromium calcium tank and two level deliming tank, the two level is removed
Calcium tank is connected by pipeline with micropore fine filtration device II, the pipeline between two level deliming tank and micropore fine filtration device II
It is equipped with infusion pump II, the outlet of micropore fine filtration device II is equipped with steam stripping ammonia-removing tower system connecting pipe.
8. the acid ammonium salt pretreatment system according to claim 7 for improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation
System, it is characterized in that：The level-one is connected with sulfuric acid storage tank except the sulfuric acid entrance of chromium calcium tank by pipeline, level-one except chromium calcium tank and
Pipeline between sulfuric acid storage tank is equipped with sulfuric acid delivery pump.
9. the acid ammonium salt pretreatment system according to claim 7 for improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation
System, it is characterized in that：The level-one is equipped with acid ammonium salt vanadium wastewater pipeline, level-one except the acid ammonium salt vanadium wastewater entrance of silicon tank
Except the acid ammonium salt vanadium wastewater inlet duct of silicon tank is equipped with valve a.
10. the acid ammonium salt pretreatment system according to claim 7 for improving the vanadic anhydride steam stripping ammonia-removing tower cycle of operation
System, it is characterized in that：The two level is equipped with valve b except the inlet duct of silicon tank, and the level-one removes silicon solution except the secondary of chromium calcium tank
Inlet duct is equipped with valve c, and the level-one is equipped with valve d except the sulfuric acid inlet duct of chromium calcium tank, and the two level deliming tank enters
Mouth pipeline is equipped with valve e.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724406A (en) * | 2005-06-20 | 2006-01-25 | 李强国 | Process for treating industrial waste water containing chromium, vanadium |
| CN102795721A (en) * | 2012-07-28 | 2012-11-28 | 中信锦州金属股份有限公司 | Treatment method for wastewater after vanadium precipitation |
| KR20130001839A (en) * | 2011-06-28 | 2013-01-07 | 정대준 | Mineral water manufacturing method |
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2018
- 2018-04-14 CN CN201810334304.XA patent/CN108640383B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724406A (en) * | 2005-06-20 | 2006-01-25 | 李强国 | Process for treating industrial waste water containing chromium, vanadium |
| KR20130001839A (en) * | 2011-06-28 | 2013-01-07 | 정대준 | Mineral water manufacturing method |
| CN102795721A (en) * | 2012-07-28 | 2012-11-28 | 中信锦州金属股份有限公司 | Treatment method for wastewater after vanadium precipitation |
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