CN104944665A - Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid - Google Patents
Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid Download PDFInfo
- Publication number
- CN104944665A CN104944665A CN201510345698.5A CN201510345698A CN104944665A CN 104944665 A CN104944665 A CN 104944665A CN 201510345698 A CN201510345698 A CN 201510345698A CN 104944665 A CN104944665 A CN 104944665A
- Authority
- CN
- China
- Prior art keywords
- hydrochloric acid
- liquor
- crystallization
- evaporation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid. The device comprises an evaporator, a separating tank, a crystallizer, a heat exchanger, an absorption tower, a waste acid tank, a reaction kettle, solid-liquid separating equipment, a dryer and a calcining furnace. According to the comprehensive resourceful treatment device and method, a new technology for comprehensive resourceful treatment of the chlorohydric acid pickling waste liquid is achieved, the advantages of being low in investment and treatment cost and low in energy consumption are achieved, the comprehensive utilization of acid and iron in the waste liquid can be achieved, environment pollution hazards brought by the chlorohydric acid pickling waste liquid are reduced, hydrochloric acid and iron salt can be recovered, nanocrystalline iron oxide with quite economic value can be prepared, and the environmental benefits and the economic benefits are well taken into account.
Description
Technical field
System of the present invention relates to offal treatment and resource technology field, particularly relates to a kind of hydrochloric acid pickling waste liquor comprehensive resource treatment unit and method.
Background technology
Pickling is a kind of method on clean metal surface, is also the necessary process of steel process for processing, its objective is the oxide compound removing metallic surface.The spent pickle liquor of outer row, not only containing high density spent acid, simultaneously containing plurality of heavy metal ion, has comparatively severe corrosive, can cause serious pollution and harm to surrounding environment.Spent pickle liquor is listed in National Hazard refuse register by Environmental Protection in China department already.Hydrochloric acid is the hydrochloric acid cleaning agent of the main flow clean-out system in steel cleaning, general acid washing rolled steel, and content of hydrochloric acid is generally 5-15%, and after pickling in the outer spent pickle liquor arranged, concentration of hydrochloric acid can reduce 75-85%, and iron concentration is then increased to 60-120g/L.
Spent pickle liquor recycling processing method mainly contains high-temperature roasting method, evaporative crystallization method, ion exchange method, chemical transformation, membrane technology etc.High-temperature roasting method resource recovery is high, and treatment effect is best, but have that front-end investment is large simultaneously, energy consumption is large, technique and equipment requirements high and limit its application in medium and small sized enterprises; Ion exchange method and membrane technology effectively can realize being separated of metal ion and acid, and equipment is simple, but its application is subject to the restriction of concentration of metal ions and there is the problem that resin and membrane module easily pollute, and therefore receives restriction in actual applications; Evaporative crystallization method is simple to operate, and processing cost is cheap, but have that vaporization temperature is high, maintenance of the equipment is difficult, exterior liquid ferric remains content cannot be up to standard etc. shortcoming.Along with going deep into of research, multiple spent pickle liquor resource treatment technique is improved further, and the raw more recycling treatment of not stopping pregnancy utilizes technology.Not only consider to reclaim the acid in spent pickle liquor, and further consider and iron is wherein recycled, as chemical transformation prepares coagulating agent and flocculation agent, brown iron oxide etc.
Summary of the invention
The present invention considers the factors such as changing rejected material to useful resource, technology difficulty and cost of investment, proposes a kind of new hydrochloric acid pickling waste liquor comprehensive resource treatment unit and method.
A kind of hydrochloric acid pickling waste liquor comprehensive resource of the present invention treatment unit, comprises vaporizer, separating tank, crystallizer, heat exchanger, absorption tower, spent acid groove, reactor, solid-liquid separating equipment, moisture eliminator, calcining furnace.
Described vaporizer is provided with charging opening, and evaporator discharge mouth is connected with condenser inlet mouth by separating tank, and condenser is provided with entrance of cooling water and outlet, and condenser air outlet is connected with the inlet mouth on the first absorption tower, and condenser material liquid outlet collects regeneration hydrochloric acid; The outlet of vaporizer raffinate is connected with crystallizer opening for feed by separating tank, crystallizer discharge port is connected with the opening for feed of centrifugal device, crystallizer is provided with entrance of cooling water and outlet, the liquid outlet opening of centrifugal device is connected with spent acid groove liquor inlet, spent acid groove material liquid outlet is connected with reactor liquor inlet, reactor pneumatic outlet is connected with the inlet mouth of second absorption tower, and reactor material liquid outlet is connected with the opening for feed of pressure filter, is provided with drying plant and calciner successively after pressure filter; Be provided with regenerating acid collector in the first described absorption tower, regenerating acid collector is replaceable.
A kind of hydrochloric acid pickling waste liquor comprehensive resources treatment method comprises the following steps:
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
Hydrochloric acid pickling waste liquor being removed after filtration large granular impurity is placed in vaporizer, passes into steam, and the vacuum tightness regulating vaporizer is 0.06MPa, under the temperature of reaction of 88 DEG C, carry out negative pressure evaporation.The HCl gas produced is by condensing works condensation reclaiming hydrochloric acid, and waste liquid evaporation amount is 50%, and condenser tail gas is absorbed by tap water circulated sprinkling in absorption tower, when the hydrochloric acid mass concentration in regenerating acid collector reaches 5%, change regenerating acid collector;
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one negative pressure evaporation technique, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
In the remaining residue mother liquor after step 2 Crystallization Separation, add the PAM solution that iron powder and mass concentration are 1%, complete pre-treatment; Then supernatant liquor is joined enamel reaction still, add ammoniacal liquor mix and blend that mass concentration is 1.5-5% and pass into air and be oxidized, stir speed (S.S.) is 300-600 r/min, and temperature of reaction is 20-40 DEG C, reaction times is 30-60min, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, and filter cake is after revolving and steaming instrument drying and crushing, and calcine 2 hours in calcining furnace, calcining temperature is 400-800 DEG C, obtains pulverous α-Fe
2o
3finished product, last remaining filtrate discharge.
The beneficial effect that the present invention has: the present invention is the novel process of a kind of hydrochloric acid pickling waste liquor comprehensive resource process, there is investment low with processing cost, low power consumption and other advantages, the comprehensive utilization of acid and iron in waste liquid can be realized, both the environmental pollution damage that hydrochloric acid pickling waste liquor brings had been decreased, recyclable hydrochloric acid and the molysite also obtained nano-sized iron oxide having pretty economical and be worth, has taken into account environmental benefit and economic benefit well again.
Accompanying drawing explanation
Fig. 1 is device schematic diagram of the present invention.
Embodiment
As shown in Figure 1, a kind of hydrochloric acid pickling waste liquor comprehensive resource treatment unit comprises vaporizer, separating tank, crystallizer, heat exchanger, absorption tower, spent acid groove, reactor, solid-liquid separating equipment, moisture eliminator, calcining furnace.
Described vaporizer is provided with charging opening, and evaporator discharge mouth is connected with condenser inlet mouth by separating tank, and condenser is provided with entrance of cooling water and outlet, and condenser air outlet is connected with the inlet mouth on the first absorption tower, and condenser material liquid outlet collects regeneration hydrochloric acid; The outlet of vaporizer raffinate is connected with crystallizer opening for feed by separating tank, crystallizer discharge port is connected with the opening for feed of centrifugal device, crystallizer is provided with entrance of cooling water and outlet, the liquid outlet opening of centrifugal device is connected with spent acid groove liquor inlet, spent acid groove material liquid outlet is connected with reactor liquor inlet, reactor pneumatic outlet is connected with the inlet mouth of second absorption tower, and reactor material liquid outlet is connected with the opening for feed of pressure filter, is provided with drying plant and calciner successively after pressure filter.
Embodiment 1
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, passes into steam, carries out negative pressure evaporation under optimal operating conditions, and namely vacuum tightness is 0.06MPa, and temperature of reaction is 88 DEG C, and waste liquid evaporation amount is 50%.The HCl gas be evaporated is reclaimed by condensing works condensation, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, remaining after crystallization 0.5t mother liquor in add iron powder 50kg(100 g/L) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, be the ammoniacal liquor mix and blend of 1.5% and pass into air with mass concentration, stir speed (S.S.) is 600r/min, and the reaction times is 30min, and temperature of reaction is 20 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution is separated through pressure filter press filtration, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 600 DEG C of calcinings 2 hours in calcining furnace, obtains Powdered α-Fe
2o
3finished product, its average crystal grain diameter is 21.8nm, Fe
2o
3content is 98.02%.
Embodiment 2
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, remaining after crystallization 0.5t mother liquor in add iron powder 50kg(100 g/L) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, be the ammoniacal liquor mix and blend of 2.5% and pass into air with mass concentration, stir speed (S.S.) is 500r/min, and the reaction times is 30min, and temperature of reaction is 40 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution is separated through pressure filter press filtration, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 600 DEG C of calcinings 2 hours in calcining furnace, obtains Powdered α-Fe
2o
3finished product, its average crystal grain diameter is 38.6nm, Fe
2o
3content is 97.92%.
Embodiment 3
Step one: negative pressure evaporation process
Negative pressure evaporation process carries out negative pressure evaporation to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 500r/min, and the reaction times is 30min, and temperature of reaction is 40 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 600 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 47.2nm, Fe
2o
3content is 99.96%.
Embodiment 4
Step one: negative pressure evaporation process
Negative pressure evaporation process carries out negative pressure evaporation to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 400r/min, and the reaction times is 30min, and temperature of reaction is 30 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 500 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 71.2nm, Fe
2o
3content is 98.41%.
Embodiment 5
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 500r/min, and temperature of reaction is 20 DEG C, and the reaction times is 30min, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 600 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 29.6nm, Fe
2o
3content is 96.81%.
Embodiment 6
Step one: negative pressure evaporation process
Negative pressure evaporation process carries out negative pressure evaporation to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 2.5% and pass into air, stir speed (S.S.) is 600r/min, and the reaction times is 45min, and temperature of reaction is 30 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 400 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 24.8nm, Fe
2o
3content is 95.08%.
Embodiment 7
Step one: negative pressure evaporation process
Negative pressure evaporation process carries out negative pressure evaporation to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 1.5% and pass into air, stir speed (S.S.) is 400r/min, and the reaction times is 60min, and temperature of reaction is 40 DEG C, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 400 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 22.5nm, Fe
2o
3content is 96.86%.
Embodiment 8
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
Mother liquid evaporation crystallisation by cooling, by the evaporated mother liquor cooling after evaporation, is separated out and reclaims iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 300r/min, and temperature of reaction is 40 DEG C, and the reaction times is 30min, is that oxygenant carries out oxidizing reaction with air.Mixed solution is separated through pressure filter press filtration, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 600 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 43.3nm, Fe
2o
3content is 97.57%.
Embodiment 9
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 500r/min, and temperature of reaction is 40 DEG C, and the reaction times is 30min, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 400 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 27.8nm, Fe
2o
3content is 98.72%.
Embodiment 10
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
1t hydrochloric acid pickling waste liquor is removed large granular impurity to be after filtration placed in vaporizer, negative pressure evaporation is carried out under the optimum operation condition described in embodiment 1, obtain the regeneration hydrochloric acid that massfraction is the left and right of 10%, the HCl gas be evaporated is reclaimed by condensing works condensation, condenser tail gas tap water circulated sprinkling absorbs, and changes and reclaim as hydrochloric acid water in acid cleaning process when concentration of hydrochloric acid reaches 5% to absorption liquid.
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one evaporating and concentrating process, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims and obtains about 0.15t FeCl
2h
2o crystallization.
Step 3: the preparation of nano-sized iron oxide
Add iron powder etc. in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3.
To evaporation, add iron powder (also can replace with scrap iron) 50kg(100 g/L in remaining 0.5t mother liquor after Crystallization Separation) and massfraction be 1% PAM solution 50g, complete pre-treatment; Then supernatant liquor is added enamel reaction still, add mass concentration and be the ammoniacal liquor mix and blend of 5% and pass into air, stir speed (S.S.) is 500r/min, and temperature of reaction is 40 DEG C, and the reaction times is 30min, is that oxygenant carries out oxidizing reaction with air.Mixed solution adopts pressure filter press filtration to be separated, filtrate qualified discharge, and filter cake, after revolving and steaming instrument drying and crushing, with 800 DEG C of calcinings 2 hours in calcining furnace, obtains pulverous α-Fe
2o
3finished product, its average crystal grain diameter is 75.8nm, Fe
2o
3content is 98.89%.
Claims (3)
1. a hydrochloric acid pickling waste liquor comprehensive resource treatment unit, comprises vaporizer, separating tank, crystallizer, heat exchanger, absorption tower, spent acid groove, reactor, solid-liquid separating equipment, moisture eliminator, calcining furnace;
It is characterized in that: described vaporizer is provided with charging opening, evaporator discharge mouth is connected with condenser inlet mouth by separating tank, condenser is provided with entrance of cooling water and outlet, and condenser air outlet is connected with the inlet mouth on the first absorption tower, and condenser material liquid outlet collects regeneration hydrochloric acid; The outlet of vaporizer raffinate is connected with crystallizer opening for feed by separating tank, crystallizer discharge port is connected with the opening for feed of centrifugal device, crystallizer is provided with entrance of cooling water and outlet, the liquid outlet opening of centrifugal device is connected with spent acid groove liquor inlet, spent acid groove material liquid outlet is connected with reactor liquor inlet, reactor pneumatic outlet is connected with the inlet mouth of second absorption tower, and reactor material liquid outlet is connected with the opening for feed of pressure filter, is provided with drying plant and calciner successively after pressure filter.
2. a kind of hydrochloric acid pickling waste liquor comprehensive resource treatment unit according to claim 1, is characterized in that: be provided with regenerating acid collector in the first described absorption tower, regenerating acid collector is replaceable.
3. the treatment process of a kind of hydrochloric acid pickling waste liquor comprehensive resource treatment unit according to claim 1, it is characterized in that, the method specifically comprises the following steps:
Step one: negative pressure evaporation process
Negative pressure evaporation is carried out to spent pickle liquor, collects condensation distillate for regeneration hydrochloric acid
Hydrochloric acid pickling waste liquor being removed after filtration large granular impurity is placed in vaporizer, passes into steam, and the vacuum tightness regulating vaporizer is 0.06MPa, under the temperature of reaction of 88 DEG C, carry out negative pressure evaporation; The HCl gas produced is by condensing works condensation reclaiming hydrochloric acid, and waste liquid evaporation amount is 50%, and condenser tail gas is absorbed by tap water circulated sprinkling in absorption tower, when the hydrochloric acid mass concentration in regenerating acid collector reaches 5%, change regenerating acid collector;
Step 2: mother liquid evaporation crystallisation by cooling
By the evaporated mother liquor cooling after evaporation, separate out and reclaim iron protochloride crystallization
In residue mother liquor after step one negative pressure evaporation technique, solute iron protochloride is in hypersaturated state, take tap water as heat-eliminating medium, and mother liquor enters cooling crystallizer cooling, separates out FeCl
2h
2o crystallization, after centrifugal device solid-liquid separation, reclaims FeCl
2h
2o crystallization;
Step 3: the preparation of nano-sized iron oxide
Add iron powder in residue mother liquor after Crystallization Separation, after reaction, obtain α-Fe through solid-liquid separation, drying, calcining
2o
3;
In the remaining residue mother liquor after step 2 Crystallization Separation, add the PAM solution that iron powder and mass concentration are 1%, complete pre-treatment; Then supernatant liquor is joined enamel reaction still, add ammoniacal liquor mix and blend that mass concentration is 1.5-5% and pass into air and be oxidized, stir speed (S.S.) is 300-600 r/min, and temperature of reaction is 20-40 DEG C, reaction times is 30-60min, is that oxygenant carries out oxidizing reaction with air; Mixed solution adopts pressure filter press filtration to be separated, and filter cake is after revolving and steaming instrument drying and crushing, and calcine 2 hours in calcining furnace, calcining temperature is 400-800 DEG C, obtains pulverous α-Fe
2o
3finished product, last remaining filtrate discharge.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510345698.5A CN104944665B (en) | 2015-06-19 | 2015-06-19 | Comprehensive resourceful treatment method for chlorohydric acid pickling waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510345698.5A CN104944665B (en) | 2015-06-19 | 2015-06-19 | Comprehensive resourceful treatment method for chlorohydric acid pickling waste liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104944665A true CN104944665A (en) | 2015-09-30 |
| CN104944665B CN104944665B (en) | 2017-04-26 |
Family
ID=54159806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510345698.5A Active CN104944665B (en) | 2015-06-19 | 2015-06-19 | Comprehensive resourceful treatment method for chlorohydric acid pickling waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104944665B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603447A (en) * | 2016-03-07 | 2016-05-25 | 环境保护部南京环境科学研究所 | Recycling process system and method for steel wire rope acid pickling waste acid |
| CN106430100A (en) * | 2016-10-19 | 2017-02-22 | 深圳泛科环保产业发展有限公司 | Continuous-production reduced pressure distillation device and process for recovering iron-containing waste acid liquid |
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN108821495A (en) * | 2018-07-25 | 2018-11-16 | 常熟市电热合金材料厂有限公司 | A kind of heating wire pickle liquor harmless treatment process and system |
| CN109626330A (en) * | 2019-01-17 | 2019-04-16 | 成都虹华环保科技股份有限公司 | The distillation recovery device and method of hydrogen chloride in a kind of acidic etching waste liquid |
| CN110853790A (en) * | 2019-11-21 | 2020-02-28 | 清华大学 | Treatment method and treatment system for production waste liquid of high-temperature gas cooled reactor fuel element |
| CN112573579A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recycling treatment process for sludge ferrous chloride on surface of metal product |
| CN112573582A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recycling treatment process for waste acid ferrous chloride on surface of metal product |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
| CN115180760A (en) * | 2022-07-13 | 2022-10-14 | 首钢集团有限公司 | Method and system for preparing desulfurizer from pickling waste liquid and application of desulfurizer |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000282272A (en) * | 1999-03-30 | 2000-10-10 | Osaka Gas Co Ltd | Treatment of waste hydrochloric acid |
| CN101798120A (en) * | 2010-02-02 | 2010-08-11 | 东南大学 | Method for producing nanometer iron oxide red by utilizing ferrous chloride recovered from waste acid washing liquor |
| CN101823767A (en) * | 2010-05-17 | 2010-09-08 | 哈尔滨师范大学 | Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor |
| WO2011072318A1 (en) * | 2009-12-17 | 2011-06-23 | Sms Siemag Process Technologies Gmbh | Method and device for producing an iron(iii) chloride solution |
| CN202072465U (en) * | 2011-05-24 | 2011-12-14 | 钱钧 | Pickling waste liquid recycling treatment device |
| CN102660751A (en) * | 2012-04-28 | 2012-09-12 | 浙江大学 | Resourceful treating method and resourceful treating device for metal pickling effluent |
| CN102689930A (en) * | 2011-03-24 | 2012-09-26 | 镇江市丹徒区江南热镀锌有限公司 | Hydrochloric acid pickling waste liquid resource integrated utilization method for preparing iron oxide and ammonium sulfate |
| CN202610337U (en) * | 2012-04-28 | 2012-12-19 | 浙江大学 | Resourceful treatment device for metal pickling waste liquor |
| CN103553256A (en) * | 2013-11-04 | 2014-02-05 | 云南农业大学 | Recycling treatment process for chlorohydric acid pickling liquid waste |
| CN204779205U (en) * | 2015-06-19 | 2015-11-18 | 浙江大学 | Resourceful treatment device is synthesized to hydrochloric acid spent pickle liquor |
-
2015
- 2015-06-19 CN CN201510345698.5A patent/CN104944665B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000282272A (en) * | 1999-03-30 | 2000-10-10 | Osaka Gas Co Ltd | Treatment of waste hydrochloric acid |
| WO2011072318A1 (en) * | 2009-12-17 | 2011-06-23 | Sms Siemag Process Technologies Gmbh | Method and device for producing an iron(iii) chloride solution |
| CN101798120A (en) * | 2010-02-02 | 2010-08-11 | 东南大学 | Method for producing nanometer iron oxide red by utilizing ferrous chloride recovered from waste acid washing liquor |
| CN101823767A (en) * | 2010-05-17 | 2010-09-08 | 哈尔滨师范大学 | Method for preparing nano ferric oxide powder material with controllable grain size with pickling waste liquor |
| CN102689930A (en) * | 2011-03-24 | 2012-09-26 | 镇江市丹徒区江南热镀锌有限公司 | Hydrochloric acid pickling waste liquid resource integrated utilization method for preparing iron oxide and ammonium sulfate |
| CN202072465U (en) * | 2011-05-24 | 2011-12-14 | 钱钧 | Pickling waste liquid recycling treatment device |
| CN102660751A (en) * | 2012-04-28 | 2012-09-12 | 浙江大学 | Resourceful treating method and resourceful treating device for metal pickling effluent |
| CN202610337U (en) * | 2012-04-28 | 2012-12-19 | 浙江大学 | Resourceful treatment device for metal pickling waste liquor |
| CN103553256A (en) * | 2013-11-04 | 2014-02-05 | 云南农业大学 | Recycling treatment process for chlorohydric acid pickling liquid waste |
| CN204779205U (en) * | 2015-06-19 | 2015-11-18 | 浙江大学 | Resourceful treatment device is synthesized to hydrochloric acid spent pickle liquor |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603447B (en) * | 2016-03-07 | 2018-03-02 | 环境保护部南京环境科学研究所 | A kind of system and method for steel wire rope acid-washing waste acid disposal of resources technique |
| CN105603447A (en) * | 2016-03-07 | 2016-05-25 | 环境保护部南京环境科学研究所 | Recycling process system and method for steel wire rope acid pickling waste acid |
| CN106430100A (en) * | 2016-10-19 | 2017-02-22 | 深圳泛科环保产业发展有限公司 | Continuous-production reduced pressure distillation device and process for recovering iron-containing waste acid liquid |
| CN107460493A (en) * | 2017-07-04 | 2017-12-12 | 当涂县宏宇金属炉料有限责任公司 | A kind of recovery and treatment method of secondary metal pickle liquor |
| CN108821495A (en) * | 2018-07-25 | 2018-11-16 | 常熟市电热合金材料厂有限公司 | A kind of heating wire pickle liquor harmless treatment process and system |
| CN109626330B (en) * | 2019-01-17 | 2022-11-01 | 虹华科技股份有限公司 | Distillation recovery device and method for hydrogen chloride in acidic etching waste liquid |
| CN109626330A (en) * | 2019-01-17 | 2019-04-16 | 成都虹华环保科技股份有限公司 | The distillation recovery device and method of hydrogen chloride in a kind of acidic etching waste liquid |
| CN110853790A (en) * | 2019-11-21 | 2020-02-28 | 清华大学 | Treatment method and treatment system for production waste liquid of high-temperature gas cooled reactor fuel element |
| CN110853790B (en) * | 2019-11-21 | 2021-12-14 | 清华大学 | Treatment method and treatment system for production waste liquid of high-temperature gas cooled reactor fuel element |
| CN112573582A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recycling treatment process for waste acid ferrous chloride on surface of metal product |
| CN112573579A (en) * | 2020-10-12 | 2021-03-30 | 江苏荣信环保科技有限公司 | Recycling treatment process for sludge ferrous chloride on surface of metal product |
| CN112897589A (en) * | 2021-02-09 | 2021-06-04 | 鞍钢股份有限公司 | Method for separating iron ions in low-alloy steel corrosion product chemical cleaning solution |
| CN115180760A (en) * | 2022-07-13 | 2022-10-14 | 首钢集团有限公司 | Method and system for preparing desulfurizer from pickling waste liquid and application of desulfurizer |
| CN115180760B (en) * | 2022-07-13 | 2023-08-15 | 首钢集团有限公司 | Method and system for preparing desulfurizing agent from pickling waste liquid and application of desulfurizing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104944665B (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104944665A (en) | Comprehensive resourceful treatment device and method for chlorohydric acid pickling waste liquid | |
| CN104263946B (en) | A kind of method reclaiming tungsten, vanadium, titanium from SCR denitration dead catalyst | |
| CN109336140B (en) | Process for extracting lithium by adding lithium iron phosphate into lepidolite | |
| CN100469697C (en) | Method for producing low-magnesium battery-stage lithium carbonate from lithium sulfate solution | |
| CN105695751B (en) | A kind of purification technique of electrolytic manganese anode mud | |
| CN103553138A (en) | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water | |
| CN109244588B (en) | Method for producing ternary precursor and high-purity lithium carbonate by using waste ternary lithium battery | |
| CN111333046B (en) | Resource recovery method and system for waste lithium iron phosphate anode based on hydrochloric acid circulation | |
| CN103787542B (en) | The wastewater recovery processing technique that a kind of Preparation of Sebacic Acid From Castor Oil produces and device | |
| CN102897810A (en) | Method for producing aluminum oxide by using fly ash | |
| CN106630313A (en) | Reduction circulation process method for recycling zinc elements in iron-containing waste acid | |
| CN111945016A (en) | Method for selectively extracting lithium from anode and cathode powder of waste lithium ion battery by roasting method | |
| CN102010082A (en) | Treatment method for recycling waste dilute sulfuric acid | |
| CN102476884A (en) | Ammonia nitrogen wastewater treatment method | |
| CN204779205U (en) | Resourceful treatment device is synthesized to hydrochloric acid spent pickle liquor | |
| CN113526546B (en) | System and method for preparing battery-grade lead oxide through clean conversion of waste lead paste | |
| CN114421044A (en) | Purification treatment method and system for phosphorus-iron slag mixture containing Al and Cu impurities | |
| CN202610337U (en) | Resourceful treatment device for metal pickling waste liquor | |
| CN102626646A (en) | Device and method for recycling cobalt-manganese catalyst in oxidation section | |
| CN203754551U (en) | Device for recycling and treating waste water produced during preparation of decanedioic acid by utilizing castor oil | |
| CN116706302A (en) | Lithium battery recycling method | |
| CN107459021B (en) | Apparatus and method for decomposing nitrate solution | |
| CN113764759B (en) | Recovery method of waste lithium battery slurry | |
| CN111321298A (en) | Method for leaching waste ternary LNCM lithium ion battery and recovering valuable metal | |
| CN213623699U (en) | Ternary precursor production washing water treatment system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200628 Address after: Room 803a, building 12, 30 Xiangyuan Road, Gongshu District, Hangzhou City, Zhejiang Province Patentee after: ZHEJIANG TIANCHUAN ENVIRONMENTAL PROTECTION TECHNOLOGY Co.,Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Xihu District, Zhejiang Road, No. 38, No. Patentee before: ZHEJIANG University |
|
| TR01 | Transfer of patent right |