CN110395816A

CN110395816A - The acid recovery and purification system of pickle liquor

Info

Publication number: CN110395816A
Application number: CN201910633536.XA
Authority: CN
Inventors: 任晓哲; 秦小伟; 周江; 钟卫权
Original assignee: Zhejiang Dongyang Environmental Engineering Co Ltd
Current assignee: Zhejiang Dongyang Environmental Engineering Co Ltd
Priority date: 2019-07-15
Filing date: 2019-07-15
Publication date: 2019-11-01
Anticipated expiration: 2039-07-15
Also published as: CN110395816B

Abstract

The present invention relates to a kind of acid recovery of pickle liquor and purification systems, belong to the Recycle Technology of Waste Water field of metal finish.It successively include spent acid sedimentation device, filter device and ion exchange resin recyclable device.Further include having the first storage tank, be set between the spent acid sedimentation device and the filter device, the second storage tank, is set between the filter device and the ion exchange resin recyclable device.Recycling and purification of the purification system for pickle liquor in metal finish industry have the advantages that the degree of purity height of cleaning acid, high efficiente callback, low energy consumption and workload is few.

Description

The acid recovery and purification system of pickle liquor

Technical field

The invention belongs to the Recycle Technology of Waste Water fields of metal finish, and in particular to a kind of acid recovery of pickle liquor and Purification system.

Background technique

Strong inorganic acid (sulfuric acid, nitric acid, hydrochloric acid etc.) is commonly used in metal finish industry to remove the oxidation of metal surface Object is to reduce its influence to subsequent production operation.Largely, these oxide epidermises be by acid dissolution, and with Be dissolved in the increase of metal concentration in acid solution, the concentration of free acid is also accordingly reduced.Although new acid can be added into acid To make up this disadvantage in liquid, but when metal concentration increases, oxide removal efficiency (pickling ability) would generally be reduced. When oxide skin can not be sufficiently removed again, these acid solutions must just be disposed the acid solution more renewed.

This operating method can reduce production efficiency.And the pickling ability for the acid solution newly prepared is very powerful, and can It can lead to over-pickling, therefore generate material may also be able to close to underproof phenomenon in turn is scrapped due to pickling.In order to Subsequent process of surface treatment problem is prevented, doing over again may be necessary.

In addition, also containing a large amount of not used or " free " acid with the pickling solution to have given up, valuable chemicals does not have It is recovered, while also will increase the difficulty of wastewater treatment.Therefore, it is badly in need of a kind of clearing machine recovery process of novel effective acid.

In the prior art, the apparatus structure for acid block technique of use is more complicated, takes up a large area, there is also trees The problems such as rouge is easily contaminated and scraps, the rate of recovery of acid is low, recovery acid impurity is more, recycling acid concentration is low, the recycling of spent acid Treatment effect is poor.

Such as application No. is 201710629752.8 Chinese invention patents to disclose a kind of waste acidity recovery method and apparatus, side Method is that spent acid is carried out sour absorption into equipped with the resin tank body for inhaling acid resin through pumping pressurization into acid after filtering, unadsorbed The waste water of saliferous drain into wastewater collection pond through water outlet；The resin tank body height≤500mm, the resin filled are spherical Particulate resin.Method provided by the invention is with the obvious advantage in terms of waste acidity recovery, has occupied area small, easy to operate, acid recovery For rate 95%, recovery acid concentrations versus has a degree of concentration in former spent acid free acid concentration, and spent acid free acid concentration exists The pure acid that 10%~15% concentration obtains can be concentrated to 20%~30%, the metal salt residual quantity of the pure acid of gained 1 gram/ It rises hereinafter, the application of enterprise can be met.

For another example application No. is 201621013666.1 Chinese utility model patent, to disclose a kind of Special Resin trundle bed useless Acid-restoring plant, including ion exchange column, waste acid pot, elution flow container, brine tank, sour collecting tank and eluent recycling can, ion The top of exchange column is equipped with eluent import and brine outlet, bottom is equipped with spent acid import and eluent exports, waste acid pot and useless The first booster pump, first flowmeter, first filter, the first valve, elution flow container and eluent import are equipped between sour import Between be equipped with the second booster pump, second flowmeter, the second filter, the second valve, between brine outlet and brine tank be equipped with PH Detector, third valve, sour collecting tank and eluent outlet between be equipped with H+ detector and the 4th valve, eluent recycling can with The connection of eluent inlet ductwork.The purpose is to: solve existing acid-restoring plant there are structures more complicated, water consumption compared with Greatly, the poor problem of the recovery processing effect of spent acid.

Summary of the invention

In view of the above-mentioned problems, the present invention provides the acid recovery and purification system of a kind of pickle liquor, it to be used for metal finish The recycling and purification of pickle liquor in industry, have that the degree of purity height of cleaning acid, high efficiente callback, that low energy consumption and workload is few is excellent Point.

Technical proposal that the invention solves the above-mentioned problems is as follows:

The acid recovery and purification system of pickle liquor successively include according to the processing sequence of pickle liquor:

Spent acid sedimentation device is tentatively removed for settling the solid phase particles in pickle liquor；

Filter device, for further removing the impurity after sedimentation in pickle liquor；

Ion exchange resin recyclable device is used for adsorption/desorption acid solution, and filtered pickle liquor is through the ion exchange resin After recyclable device, acid is adsorbed, effluent brine progress wastewater treatment, after the ion exchange resin recyclable device adsorber acid, then it is defeated Enter water to be desorbed, forms acid solution, send pickling system back to；

Also include:

First storage tank is set between the spent acid sedimentation device and the filter device, for accepting the spent acid sedimentation dress The supernatant pickle liquor of outflow is set, and is stored wait enter the filter device；

Second storage tank is set between the filter device and the ion exchange resin recyclable device, for accepting the mistake The filtering pickle liquor of device outflow is filtered, and is stored wait enter the ion exchange resin recyclable device.

As a preferred embodiment of the above technical solution, the filter device is U-shaped hollow fiber membrane filtration device, includes:

Putamina is provided on the putamina and produces the mouth of a river, concentrated water spout and backwash discharge outlet；

Upper head plate, the upper area being set in the putamina；

Central tube, is set in the putamina and the perforation upper head plate, and the central tube upper end is provided with water inlet, on tube wall It is provided with the first water distributing pore；

At least two film support frames, interval are arranged on the position that the central tube is located at below the upper head plate, and described Film support frame is connected with the central tube, is provided with film fixation hole and the second water distributing pore on the film support frame, and described second A part of opening direction in water distributing pore is directed toward the putamina upper end；

Hollow-fibre membrane, both ends are fixed on the upper head plate, and both ends are connected with the region above the upper head plate Logical, the membrane tube of the hollow-fibre membrane passes through the film fixation hole and is limited in the putamina.

Herein described up and down direction is the same as the up and down direction in Figure of description 2-4.

It is provided with water distributing pore on central tube and film support frame, and includes that film is directed toward in outs open direction on film support frame The water distributing pore of shell upper end enables to water distribution more uniform, avoid material liquid water distribution it is irregular caused by film bearing up-down force And suffered concentration difference different problems.

As a preferred embodiment of the above technical solution, the production mouth of a river is set on the outer wall of the putamina, and the position of the outer wall It sets and is located on the upper head plate.

As a preferred embodiment of the above technical solution, the concentrated water spout is set on the outer wall of the putamina, and the position of the outer wall It sets positioned at the lower section of the hollow-fibre membrane.

As a preferred embodiment of the above technical solution, the backwash discharge outlet is set to the bottom end of the putamina.

As a preferred embodiment of the above technical solution, the upper head plate is poured by epoxy resin into integrated end plate.

As a preferred embodiment of the above technical solution, the lower end closed of the central tube.

As a preferred embodiment of the above technical solution, the film support frame is made of several outwardly extending support rods, the film Fixation hole and second water distributing pore are set on the support rod.

As a preferred embodiment of the above technical solution, second cloth according to sequence from top to bottom, on the film support frame The quantity in water hole gradually increases.

As a preferred embodiment of the above technical solution, according to sequence from top to bottom, the film support frame upper opening direction is directed toward The quantity of second water distributing pore of the putamina lower end gradually increases.

More downward, the quantity that the second water distributing pore of putamina lower end is directed toward in film support frame upper opening direction gradually increases, in addition to Water distribution is more uniform outer when enabling to filter, additionally it is possible to so that aeration when recoil cleaning is more uniform, be aerated to film surface The cleaning effect of dirt is more preferable.

As a preferred embodiment of the above technical solution, in the putamina, it is provided with a dirt below the hollow-fibre membrane and leads Chute, the dirt diversion trench are funnel-form, and bore is gradually reduced from top to bottom, and dirt diversion trench is in particular for solid-liquid point The collection and removal for the solid matter (such as metal oxide particle) for being in vitro, such substance viscosity is larger, and it is necessary to have lead It is collected and is discharged to the diversion trench of structure.

As a preferred embodiment of the above technical solution, the ion exchange resin recyclable device is using strong alkalinity anion exchange tree Rouge.

It is preferred that Tulsion A-853E, particle size range 0.1nm~0.3mm, resin framework is crosslinked polystyrene.

As a preferred embodiment of the above technical solution, the ion exchange resin recyclable device uses short resin bed.

As a preferred embodiment of the above technical solution, water distributor is provided in the ion exchange resin recyclable device.

As a preferred embodiment of the above technical solution, the resin bed in the ion exchange resin recyclable device is fixing resin Bed.

As a preferred embodiment of the above technical solution, the ion exchange resin recyclable device is realized in such a way that adverse current is intake The desorption of acid.

In conclusion the invention has the following advantages:

The application provides the acid recovery and purification system of a kind of pickle liquor, time for pickle liquor in metal finish industry It receives and purifies, can continuously remove metal ion, supplement concentrated acid, it is ensured that acid concentration in descaling bath improves pickling speed, guarantees to produce Quality；Cooperate Automatic Control, workload and sour dosage can be reduced；The base amount and dirt of pickling waste waters processing can also be reduced Mud yield, and daily operating cost is cheap, waste acid treatment per ton only consumes one ton of pure water and kilowatt-hour.

The stabilization and circular treatment of pickling solution make the pickling ability of pickling solution be maintained at a moderate state, Ke Yiti For bringing advantage for steel manufacturer:

1. reducing rework rate, Uniform Product quality；

2. increasing average pickling speed, metal ion can be continuously removed, supplements concentrated acid, it is ensured that acid concentration in descaling bath mentions High 30% or more pickling speed；

3. reducing chemical cost, dissociate acid recovering rate > 90%；

4. reducing waste processing requirement, the discharge of 98% or more spent acid is reduced；

5. structure is simple, occupied area is small, about 20-30 square metres, about 500,000 yuan of cost of investment, recycle the operation of one ton of spent acid at This about 0.8 yuan；

6. waste acidity recovery and recycling and wastewater treatment no longer need to add a large amount of alkali.

Detailed description of the invention

Fig. 1 is acid recovery and the purification system schematic diagram of pickle liquor；

Fig. 2 is U-shaped hollow fiber membrane filtration device schematic diagram；

Fig. 3 is U-shaped hollow fiber membrane filtration device the schematic diagram of the section structure；

Fig. 4 is film support frame structure diagram；

Fig. 5 is spent acid sedimentation device structural schematic diagram as described in example 2；

Fig. 6 is precipitation adsorption plate structural schematic diagram as described in example 2；

Fig. 7 is ion exchange resin recyclable device structural schematic diagram described in embodiment 3；

Fig. 8 is velocity hooster structural schematic diagram described in embodiment 3；

Fig. 9 is pressure inlet structural schematic diagram described in embodiment 3；

In figure, a- spent acid sedimentation device, a-1- hand basket, a-2- precipitation adsorption portion, a-2.1- precipitation adsorption plate, b- filter device, 1- putamina, 1-1- produce the mouth of a river, 1-2- concentrated water spout, 1-3- backwash discharge outlet, 2- upper head plate, 3- central tube, 3-1- water inlet, 3-2- First water distributing pore, 4- film support frame, 4-1- film fixation hole, the second water distributing pore of 4-2,4-3- support rod, 5- hollow-fibre membrane, 6- are dirty Object diversion trench, c- ion exchange resin recyclable device, c-1- velocity hooster, c-1.1- gathering portion, c-1.2- speedup port, c-2- increase Pressure pipe, c-2.1- diffusion part, c-2.2- pressurization port, the first storage tank of d-, the second storage tank of e-.

Specific embodiment

The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Embodiment in the present invention, ordinary skill Personnel's all other embodiment obtained under the premise of not doing creative work, shall fall within the protection scope of the present invention.

With embodiment, the present invention is described in detail with reference to the accompanying drawing.

Embodiment 1: Fig. 1 is referred to, a kind of acid recovery and purification system of pickle liquor, the system is for handling metal finishing The acid-bearing wastewater of industrial and commercial bank's industry, such waste water include phosphoric acid (20-30%), sulfuric acid (5%), nitric acid (1-2%), aluminium: >=75mg/L, chromium: >=5mg/L and nickel >=6mg/L, system spent acid to be recycled of the present invention based on phosphoric acid (weak acid), and it is well known that acid Radical ion adsorbs affinity and Acidity is proportional, and strong acid radical ion electronegativity is big, easier by resin adsorption, and weak Acid ion electronegativity is small, than less easily by resin adsorption；

Pickle liquor is in sequence followed by spent acid sedimentation device a, the first storage tank d, filter device b, the second storage tank e and ion Exchanger resin recyclable device c；

Wherein, spent acid sedimentation device a is used to that solid phase particles in pickle liquor to be made to settle tentatively to be removed, the medicament used for Sodium hydroxide and PAC, sediment are usually aluminium hydroxide, nickel hydroxide and chromium hydroxide；

First storage tank d is used to accept the supernatant pickle liquor of spent acid sedimentation device a outflow, and is stored wait enter the filtering Device b；

With reference to Fig. 2 ~ Fig. 4, filter device b is U-shaped hollow fiber membrane filtration device, by putamina 1, the upper end being arranged in putamina 1 Plate 2, central tube 3, several film support frames 4 and the hollow-fibre membrane 5 of U-shaped setting are constituted.

Wherein, the top of putamina 1, which is provided with, produces mouth of a river 1-1, and lower part is provided with concentrated water spout 1-2 and backwash discharge outlet 1-3, on The top of putamina 1 is arranged in by epoxy resin through pouring for end plate 2, and the upper end of central tube 3 is provided with water inlet 3-1, and central tube 3 is worn Upper head plate 2 is crossed, several first water distributing pore 3-2 are provided on tube body, several film support frames 4, film support frame 4 are provided on putamina Quantity be usually 3 ~ 5, the film fixation hole 4-1 for limiting hollow-fibre membrane 5 and several is provided on film support frame 4 Two water distributing pore 4-2, wherein on single film support frame 4, the quantity and opening direction of the second water distributing pore 4-2 is directed toward putamina 1 The quantity of second water distributing pore 4-2 is increased in accordance with the order from top to bottom.

1 lower part of putamina also includes a dirt diversion trench, for collecting the solid matter of concentrated water in filter process, and is discharged Outside putamina 1.

When filtering, raw water is flowed by the water inlet 3-1 of central tube 3, is flowed through the first water distributing pore 3-2 and the second water distributing pore 4-3 Enter into putamina 1, after the filtering of hollow-fibre membrane 5, water purification is discharged through producing mouth of a river 1-1 output, concentrated water by concentrated water spout 1-2；

When backwash, backwash water enters carry out backwash by 5 end of hollow-fibre membrane of 2 top of upper head plate, meanwhile, lead in central tube 3 Enter compressed air, compressed air carries out backwash aeration by the first water distributing pore 3-2 and the second water distributing pore 4-3, washes away doughnut The dirt of 5 surface adhesion of film.

Second storage tank e is used to accept the filtering pickle liquor of filter device b outflow, and is stored wait enter ion exchange Resin recovery device c；

Ion exchange resin recyclable device c uses short resin bed, and resin is fixed in resin bed, and in such a way that adverse current is intake It realizes the desorption of acid, fills strong-base anion-exchange resin in resin bed, be additionally provided with water distributor, strong alkalinity anion exchange The preferred Tulsion A-853E of resin, particle size range 0.1nm~0.3mm, resin framework is crosslinked polystyrene.

Embodiment 2: refer to Fig. 1, Fig. 5 and Fig. 6, a kind of acid recovery and purification system of pickle liquor, not with embodiment 1 It is with place: is provided with a dismountable hand basket a-1 in the spent acid sedimentation device a, is arranged at the bottom surface of the hand basket a-1 There is the precipitation adsorption portion a-2 of a multi-pore structure, if the precipitation adsorption portion a-2 is had the precipitation adsorption plate a- of hole by dry plate 2.1 constituting.

In actual use, if precipitation adsorption plate a-2.1 described in dry plate is superimposed inside the precipitation adsorption portion a-2 to be formed by staggeredly Pore structure constitute, the pore structure make the sediment based on aluminium hydroxide, nickel hydroxide and chromium hydroxide be easy inhale It is attached in hole, meanwhile, staggered pore structure supports each other, so that sediment is not easy that the precipitation adsorption portion a-2 is desorbed out, When precipitation adsorption to a certain extent when, only need to take out the hand basket a-1, at this point, due to precipitation adsorption portion a-2 overall structure protect Hold intact, sediment can be taken out of together, after taking out of, if then by precipitation adsorption plate a-2.1 described in the dry plate being superimposed points It does not take out, the overall structure of precipitation adsorption portion a-2 is destroyed at this time, and sediment will readily be scattered or be scraped, sediment After being collected, if then precipitation adsorption plate a-2.1 described in dry plate is folded to the bottom for being placed on the hand basket a-1, place into described In spent acid sedimentation device a.

The precipitating collection structure have structure is simple, collection efficiency is high, precipitating is easily separated and advantage easy to operate, solution Precipitating collection efficiency is low in traditional spent acid sedimentation device a, collects the big problem of difficulty.

Embodiment 3: Fig. 1, Fig. 7, Fig. 8 and Fig. 9, a kind of acid recovery and purification system of pickle liquor, with embodiment 1 are referred to The difference is that: several velocity hoosters c-1, institute are provided at the feed liquid port of the ion exchange resin recyclable device c It states velocity hooster c-1 to be successively made of gathering portion c-1.1 and speedup port c-1.2 according to the direction of feed solution flow, the gathering portion C-1.1 is a Duan Guanti, and according to the flow direction of feed liquid, its internal diameter is gradually reduced, the speedup port c-1.2 and the ion It is connected inside exchanger resin recyclable device c；

Several pressure inlets c-2, the pressure inlet c-2 are provided at the material liquid outlet of the ion exchange resin recyclable device c It is successively made of diffusion part c-2.1 and pressurization port c-2.2 according to the direction of feed solution flow, the diffusion part c-2.1 is one section Tube body, according to the flow direction of feed liquid, its internal diameter is gradually increased, the pressurization port c-2.2 and ion exchange resin recycling It is connected outside device c；

When feed liquid is entered in the ion exchange resin recyclable device c by velocity hooster c-1 described in several, in gathering portion c-1.1 Under the action of, pressure is gradually reduced and flow velocity is gradually increased, the turbulence effect in the ion exchange resin recyclable device c Enhanced, thus weak acid root is easier to be ion exchanged resin and be adsorbed, adsorption efficiency is higher；

When feed liquid is flowed out outside the ion exchange resin recyclable device c by pressure inlet c-2 described in several, in diffusion part c-2.1 Under the action of, pressure gradually increases and flow velocity is gradually reduced, and the pressure head outside the ion exchange resin recyclable device c is able to Enhancing can reduce the energy consumption of outer delivery pump, save operating cost.

Claims

1. the acid recovery and purification system of pickle liquor, which is characterized in that according to the processing sequence of pickle liquor, successively include Have:

Spent acid sedimentation device (a) is tentatively removed for settling the solid phase particles in pickle liquor；

Filter device (b), for further removing the impurity after sedimentation in pickle liquor；

Ion exchange resin recyclable device (c) is used for adsorption/desorption acid solution, and filtered pickle liquor is through the ion exchange After resin recovery device (c), acid is adsorbed, and effluent brine carries out wastewater treatment, ion exchange resin recyclable device (c) absorption It after acid, then inputs water and is desorbed, form acid solution, send pickling system back to；

Also include:

First storage tank (d) is set between the spent acid sedimentation device (a) and the filter device (b), described useless for accepting The supernatant pickle liquor of acid deposition device (a) outflow, and stored wait enter the filter device (b)；

Second storage tank (e) is set between the filter device (b) and the ion exchange resin recyclable device (c), for holding The filtering pickle liquor of filter device (b) outflow is connect, and is stored wait enter the ion exchange resin recyclable device (c).

2. the acid recovery and purification system of pickle liquor according to claim 1, it is characterised in that: the filter device (b) it is U-shaped hollow fiber membrane filtration device, which is characterized in that include:

Putamina (1) is provided on the putamina (1) and produces the mouth of a river (1-1), concentrated water spout (1-2) and backwash discharge outlet (1-3)；

Upper head plate (2), the upper area being set in the putamina (1)；

Central tube (3) is set in the putamina (1) and penetrates through the upper head plate (2), and central tube (3) upper end is provided with The first water distributing pore (3-2) is provided on water inlet (3-1), tube wall；

The setting of at least two film support frames (4), interval is located at the position below the upper head plate (2) in the central tube (3) On, and the film support frame (4) is connected with the central tube (3), is provided with film fixation hole (4- on the film support frame (4) 1) and the second water distributing pore (4-2), a part of opening direction in second water distributing pore (4-2) is directed toward putamina (1) upper end；

Hollow-fibre membrane (5), both ends are fixed on the upper head plate (2), and both ends are and above the upper head plate (2) Region is connected, and the membrane tube of the hollow-fibre membrane (5) passes through the film fixation hole (4-1) and is limited in the putamina (1).

3. the acid recovery and purification system of pickle liquor according to claim 1, it is characterised in that: the amberlite Rouge recyclable device (c) uses strong-base anion-exchange resin.

4. the acid recovery and purification system of pickle liquor according to claim 1 or 3, it is characterised in that: the ion is handed over It changes resin recovery device (c) and uses short resin bed.

5. the acid recovery and purification system of pickle liquor according to claim 1 or 3, it is characterised in that: the ion is handed over It changes in resin recovery device (c) and is provided with water distributor.

6. the acid recovery and purification system of pickle liquor according to claim 1 or 3, it is characterised in that: the ion is handed over The resin bed changed in resin recovery device (c) is fixing resin bed.

7. the acid recovery and purification system of pickle liquor according to claim 1 or 3, it is characterised in that: the ion is handed over Change the desorption that resin recovery device (c) realizes acid in such a way that adverse current is intake.

8. the acid recovery and purification system of pickle liquor according to claim 2, it is characterised in that: the film support frame (4) it is made of several outwardly extending support rods (4-3), the film fixation hole (4-1) and second water distributing pore (4-2) setting In on the support rod (4-3).

9. the acid recovery and purification system of pickle liquor according to claim 8, it is characterised in that: according to from top to bottom Sequentially, the quantity of second water distributing pore (4-2) on the film support frame (4) gradually increases.

10. the acid recovery and purification system of pickle liquor according to claim 8 or claim 9, it is characterised in that: according to from up to Under sequence, second water distributing pore (4-2) of putamina (1) lower end is directed toward in film support frame (4) the upper opening direction Quantity gradually increases.