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(19) State Intellectual Property Office of the People’s Republic of China

(12)Invention patent application

(10) Application publication numberCN 111499056 A

(43) Application announcement date2020.08.07

(21)Application number202010347674.4

(22)Application date2020.04.28

(71)ApplicantNanjing University of Science and Technology

addressXiaolingwei, Xuanwu District, Nanjing City, Jiangsu Province 210094

Street No. 200, Xiaolingwei Street

(72)InventorHan Weiqing Cui Tao Liu Run Wei Kajia Li Wei

Wang Lianjun Liu Xiaodong Sun Xiuyun

Li Jiansheng Shen Jinyou

(74)Patent agencyJiangsu Ruitu Law Firm 32346 agent

Wang Yujiao Chen Bin

(51)Int.Cl.
C02F 9/06(2006.01)
C02F 9/10(2006.01)
C02F 101/34(2006.01)

1 page of claims, 10 pages of description, 4 pages of drawings

(54)Invention title

An advanced treatment system for water reuse in fine chemical tail water

systems and methods

(57)Abstract

The invention discloses a water reuse method in fine chemical tail water

In-depth processing systems and methods,Belongs to fine chemical industry water reuse

Process technology field. The depth processing system consists of several stages in sequence

Combined double oxidation device, sedimentation tank and reverse osmosis device; The pair
The oxidation device includes electrocatalytic oxidation devices connected in sequence and interconnected.

Dayton oxidation unit and narrow channel electrochemical oxidation unit. double oxide

The device can efficiently remove COD from fine chemical tail water. After much

After the combined treatment of the double oxidation device and the reverse osmosis device, owned
Fresh water can be reused as recycled industrial water, and concentrated water can be evaporated

back,
The salt can be used as by-product salt after recrystallization.realize enterprise

There is nearly zero discharge of waste water and waste salt.

CN 111499056 A
CN 111499056 A claims 1/1 page

1. An advanced treatment system for water reuse in fine chemical tail water, It is characterized by:Including several levels connected in series

Double oxidation device, sedimentation tank and reverse osmosis device; The double oxidation device includes electrocatalytic oxidation devices connected in sequence and interconnected.

Dayton oxidation unit and narrow channel electrochemical oxidation unit.

2. The advanced treatment system for water reuse in fine chemical tail water according to claim 1, It is characterized by:The narrow

The distance between the anode and cathode of the channel electrochemical oxidation unit is 1 to 3 cm.

3. The advanced treatment system for water reuse in fine chemical tail water according to claim 2, It is characterized by:The narrow

Ti/PbO2Electrode
The anode of the channel electrochemical oxidation unit is selected from titanium matrix ruthenium dioxide microporous membrane electrode, or IrO2-Ta2O5electricity

one of the extremes;

And/or the electrode of the electrochemical oxidation unit is a plate electrode or a tubular electrode; and/or the flow mode of

the electrolyte in the electrochemical oxidation unit is a parallel flow mode or a through flow mode. 4. The advanced treatment

system for water reuse in fine chemical tail water according to claim 3, It is characterized by:The narrow

The anode of the channel electrochemical oxidation unit is a titanium-based ruthenium dioxide microporous tubular membrane electrode. The pore diameter is 10 to 50 microns;
cathode

The electrolyte flow mode in the electrochemical oxidation unit is a through flow mode.
For titanium tube;

5. The advanced treatment system for water reuse in fine chemical tail water according to claim 2, It is characterized by:Said Shen

The sedimentation tank is selected from inclined One of vertical flow

tube sedimentation sedimentation
tank, tanks or radial flow sedimentation tanks.

6. A method for deep treatment of water reuse in fine chemical tail water,It is characterized by:Includes the following steps:

S1 adjusts the pH of fine chemical tailwater to acidic;

S2 The fine chemical tailwater treated in step S1 enters the electrocatalytic Fenton oxidation unit. Electrolysis produces Fe2+back, add
H2O2T,urn on the narrow channel electrochemical oxidation unit to carry out in-depth COD treatment of fine chemical tailwater; After the
effluent from step S2 of S3 is settled in the sedimentation tank,Enter the reverse osmosis device;

In step S4, the concentrated water of the reverse osmosis device in step S3 is circulated and processed in step S1. The produced water is discharged.

7. The method for deep treatment of water reuse in fine chemical tail water according to claim 6, It is characterized by:described

In step S2,During the last period of electrolysis in the electrocatalytic Fenton oxidation unit, the power supply of the electrochemical oxidation unit is turned on. transport

After a certain period of time,

Then turn off the power of the electrocatalytic Fenton oxidation unit, Add H2O2Then continue to run the electrochemical oxidation process.

8. The method for deep treatment of water reuse in fine chemical tail water according to claim 7, It is characterized by:described

The current density of the electrochemical oxidation unit in step S2 is 5~25mA/cm2, The electrochemical oxidation time is 2 to 24 hours;

and/or the electrocatalytic Fenton current density in step S2 is 5~25mA/cm2, The electrolysis time is 2 to 12 hours.

9. The method for deep treatment of water reuse in fine chemical tail water according to claim 7, It is characterized by:described

Fine chemical tail water contains TDS with a concentration greater than 500mg/L.

10. The method for deep treatment of water reuse in fine chemical tail water according to any one of claims 6 to 9,

It is characterized by:After the water quality treated in step S2 reaches the reuse standard, The concentrated water after being treated by the reverse osmosis device enters

The evaporation device performs evaporation.

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CN 111499056 A manual 1/10 pages

An advanced treatment system and method for water reuse in fine chemical tail water

Technical field

[0001] The invention belongs to the technical field of water reuse technology in fine chemical tail water. more specifically,involves a refinement

Advanced treatment system and method for water reuse in industrial tail water.

Background technique

[0002] Reclaimed Water Reuse, Industrial wastewater undergoes advanced technical treatment. Remove polluted water

of organic matter and salt,Reduce COD in water bodies,TDS,conductivity,

SS, hardness,ammonia nitrogen,
Meet recycled water quality standards.

[0003] In view of the unique refractory water quality characteristics of high-salt fine chemical production wastewater, Commonly used:
"anaerobic biochemistry

(Including anaerobic hydrolysis or anaerobic digestion) - aerobic biochemistry - wastewater advanced treatment" combined process approach. The
at present, latest
The principle is to introduce dissolved air flotation and Ozone catalytic oxidation,Iron-carbon micro-electrolysis technology is coming to high-end
electrocatalytic oxidation,

Concentration of pharmaceutical wastewater for pretreatment, In order to accelerate the degradation of some refractory organic matter and improve the biodegradability of some wastewater

The subsequent treatment process is combined with the corresponding activated sludge process (AO process, SBR process, CASS process, A2O process), MBR treatment
transformation,

technology and advanced treatment technology (activated carbon filtration, ultrafiltration,

Reverse osmosis) and other process technologies are combined to form a combination

This
craftsmanship, is used to achieve effective treatment of high-concentration refractory organic wastewater. However, This type of combined process is also due to its

process growth,The complexity of the process composition increases, The area occupied increases,The number of equipment increases,
Equipment failure rate is high, equipment

High energy consumption,

Reasons such as the high degree of equipment automation,This has become a key limiting factor in the popularization and application of this combination processing technology.

Contents of the invention

[0004] 1.Problems to be solved

[0005] Aiming at the treatment process of water reuse in fine chemical tailwater containing high salt and refractory organic matter in the existing technology

The problem of low removal efficiency of medium-sized organic pollutants,The invention provides an advanced treatment system for water reuse in fine chemical tail water.

and methods,A dual oxidation device is formed by setting up an electrocatalytic Fenton oxidation unit and a narrow channel electrochemical oxidation unit that are connected in sequence and

communicate with each other. The complex formed by the organic small molecules formed after electrocatalytic Fenton oxidation and iron ions is broken in the

narrow channel electrochemical oxidation unit. Improve the Fenton oxidation efficiency of COD in fine chemical tailwater containing high salt; further
Through reverse osmosis treatment,
Realize reclaimed water reuse;In the prior art, the raw tail water containing COD that is difficult to reduce is directly evaporated to obtain pure salt.

The degree isCannot

low, be used as by-product salt, cannot be used, By setting several levels in series
It can only be regarded as a problem of hazardous waste disposal.

Double oxidation device, sedimentation tank and reverse osmosis device, Multi-level processing can reduce COD to reuse standards. After RO treatment,
The concentrated water evaporates to obtain high-purity salt, Can be used as by-product salt,
Reduce the pressure of hazardous waste treatment on enterprises.

[0006] The present invention further turns on the power supply of the electrochemical oxidation unit during the last period of electrolysis in the

electrocatalytic Fenton oxidation

Then unit,
turn off the power supply of the electrocatalytic Fenton oxidation unit,Add H2O2Then continue to run the electrochemical oxidation

Procedure. Effectively prevents the generated ferrous iron ion catalyst from being oxidized into ferric iron ions by dissolved oxygen in the water body. some time in advance

The time will turn on the power supply of the electrochemical oxidation tubular reactor.Enables ferric ions to be reduced to ferrous ions at the cathode to ensure

Efficient performance of electrocatalytic Fenton oxidation reaction.

[0007] 2.Technical solutions

[0008] In order to solve the above problems,

The technical solutions adopted by the present invention are as follows:

[0009] An advanced treatment system for water reuse in fine chemical tail water, It includes several stages of double oxidation equipment connected in series

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CN 111499056 A manual Page 2/10

The double oxidation device includes electrocatalytic Fenton oxidation units connected in sequence and interconnected.
installation, sedimentation tank and reverse osmosis device;

element and narrow channel electrochemical oxidation unit. The fine chemical tailwater after removing COD through the double oxidation device passes through the sedimentation tank to remove

Then it enters the reverse osmosis (RO) device to separate the high concentration salt in the fine chemical tail water.When the COD of concentrated water failscontinue
iron sludge. to standard,
to meet the return

to the double oxidation unit for processing.

[0010] Highly active Fe produced using electrocatalytic Fenton oxidation technology2+Catalysts and H2O2reaction, macromolecular organic matter

Thereby improving the sustainability of degrading wastewater COD,

Oxidized into small molecular organic compounds, At the same time, electrochemical oxidation technology is used to produce

Strong oxidants further remove COD from wastewater. In the electrocatalytic Fenton oxidation unit, iron loses electrons at the anode to generate ferrous ions. Should

The iron ions formed after the oxidation of ferrous ions will form complexes with organic acids and organic matter degradation intermediates. thereby reducing phen

The efficiency of oxidation;In the present invention, a narrow-channel electrochemical oxidation unit connected in series with the electrocatalytic Fenton oxidation unit can cause

the complex of iron ions to be decomposed at the anode of the narrow-channel electrochemical oxidation unit. at the same time,
Since the distance between cathode and anode is small (i.e. narrow

aisle), The broken iron ions approach the cathode under the action of turbulence and are reduced to ferrous ions at the cathode.Continue to Fenton Oxygen

chemical reaction,
Therefore, the degradation efficiency of COD can be greatly improved.

[0011] Preferably,The distance between the anode and cathode of the narrow channel electrochemical oxidation unit is 1 to 3 centimeters. Experiment find-outs, yin and yang

When the pole spacing is between 1 and 3 cm,The COD removal rate is high, This is due to the narrow passage,Plus the water flow cycle operation produces

turbulence effect,This makes the iron (III) formed after the anode breaks the complex easier to collide with the cathode surface, After iron(III) comes into contact with the cathode

Can be reduced to iron(II),The converted iron (II) can enter the electrocatalytic Fenton oxidation step with the water flow to continue to act as a catalyst.

use, Continue with H2O2The reaction generates a strong oxidizing agent ·OH to attack the remaining organic matter; The carboxylate after breaking the complex can be directly used in electrochemical

The anode surface of the chemical oxidation unit is oxidized through direct oxidation (electrons obtained from the anode surface directly degrade organic matter) or indirect oxidation (·OH is

generated on the anode surface, Degradation of organic matter by ·OH) is further degraded, It can also enter the electrocatalytic Fenton oxidation reaction body with the water flow.

The system is further oxidized by ·OH.

[0012] Preferably,The fine chemical tailwater includes pesticides,Produced during the production of pharmaceuticals or new materials and their intermediates
One or more species in the tailwater.

[0013] Preferably,The anode of the narrow channel electrochemical oxidation unit is selected from titanium matrix ruthenium dioxide microporous membrane electrode, Ti/
PbO2Electrode or IrO2-Ta2O5Electrode is one of the Dimension stable anode (DSA electrode);
[0014] And/or the electrode of the electrochemical oxidation unit is a plate electrode or a tubular electrode; and/or the electrolyte flow mode in the

[0015] electrochemical oxidation unit is a parallel flow mode (Flow-by mode) or a through-flow mode.

Flow-through mode;
[0016] And/or the cathode is made of titanium tube or stainless steel.

[0017] Preferably,The anode of the narrow channel electrochemical oxidation unit is a titanium matrix ruthenium dioxide microporous tubular membrane electrode, hole
The diameter is 10~100 microns,Preferably, it is 10 to 50 microns;The cathode is a titanium tube;
The electrolyte flow method in the electrochemical oxidation unit

The formula is the penetrating flow mode.

[0018] Preferably,The anode of the narrow-channel electrochemical oxidation unit can be prepared by flow electrodeposition or vacuum-
induced sintering of precursors. The cathode is made of titanium tube or stainless steel that has been pretreated by pickling.

[0019] For example, the titanium-based ruthenium dioxide microporous tubular membrane electrode anode can use flow electrodeposition. the electrodeposition solution

Pump into the tubular reactor,Cycles in the power-on state,Made of high specific surface area,
“Turbulent” morphological coatings and high electrical

Chemically durable titanium-based metal oxide tubular anodes.

[0020] in, The advantage of titanium matrix ruthenium dioxide microporous tubular membrane electrode as anode lies in its unique micron-scale membrane

structure (10~50μm). In addition to its good electrocatalytic oxidation performance, It also has membrane filtration function.Since the processing of the present invention

Like fine chemical tail water,SS is generally lower,Therefore, the tubular membrane electrode and the penetration flow mode are integrated into external
one, driving forces

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CN 111499056 A manual Page 3/10

Under the action of force the molecules of refractory pollutants to collide with and penetrate the anode surface, Enhanced mass transfer efficiency, cause pollution

in
The biodegradation efficiency increases, addition,
Membrane filtration retains part of the solid suspended matter,Improved effluent water quality.

[0021] Preferably,The anode of the electrocatalytic Fenton oxidation unit uses reducing iron powder. After grinding to 80-160 mesh,press
After being made into a plate shape, it is sintered using powder metallurgy technology. Made into porous composite iron electrode, This electrode has many active sites, Oxidation

Strong performance; And

The cathode is made of hydrophobic material with strong reducing properties. using vacuum induction, Sintering and other technologies are used to modify graphite electrodes

sex,A modified graphite electrode with strong reducing performance is produced.

[0022] Preferably,The sedimentation tank is selected from the group consisting ofOne of vertical
inclined flow sedimentation
tube sedimentation tanks, tanks or radial flow sedimentation tanks.

[0023] Preferably,The double oxidation devices connected in series,The sedimentation tank and reverse osmosis device are connected in series in several
everystages.
level

The concentrated water in the reverse osmosis unit is adjusted to be acidic and H is added2O2Enter the double oxidation device for processing. By connecting the double oxidation

devices in series,The sedimentation tank and reverse osmosis device are set up in several stages.Fine chemical tailwater undergoes a process of treatment in the following devices: pair
Oxidation device - sedimentation tank - reverse osmosis device - (concentrated water) - double oxidation device - sedimentation tank - reverse osmosis device - (concentrated water)…, Tool
The number of series series depends on the water quality conditions.
Ensure that the COD in the final RO concentrated water reaches GB/T19923-2005 "Urban Wastewater Recycling Utilization"

Just use the relevant water quality reuse standards in Industrial Water Quality; Efficient removal of fines through double oxidation and sedimentation tank installations

Residual biologically refractory organic pollutants (such as nitrogen- and oxygen-containing heterocyclic compounds, etc.) in industrial tailwater, The effluent then passes through reverse osmosis

The COD in the concentrated water after multi-stage RO has been reduced to the reuse standard. Steam the concentrated water
The device enables the produced water (fresh water) to be reused,

The obtained dry component salt has high purity, Can be used as by-product salt. The condensed water after evaporation can be directly reused. Achieve refinement
After sending,

Recycling and near-zero discharge of industrial tail water.

[0024] The invention also provides a method for deep treatment of water reuse in fine chemical tail water, Includes the following steps:

[0025] S1 adjusts the pH of fine chemical tailwater to acidic;

[0026] S2 The fine chemical tailwater treated in step S1 enters the electrocatalytic Fenton oxidation unit. Electrolysis produces Fe2+back, cast
Add H2O2Open
, the narrow-channel electrochemical oxidation unit to carry out in-depth COD treatment of fine chemical tailwater;
[0027] Enter
After the effluent from step S2 in S3 is settled in the sedimentation tank, the reverse osmosis device;

[0028] In step S4, the concentrated water of the reverse osmosis device in step S3 is circulated and processed in step S1. The produced water is discharged.

[0029] Preferably,In the step S2, The electrolysis is started during the last period of electrolysis in the electrocatalytic Fenton oxidation unit.
Add
After running for a specific time,Then turn off the power of the electrocatalytic Fenton oxidation unit,
Power supply for chemical oxidation unit, H2O2continue after

Run the electrochemical oxidation process. During the electrocatalytic Fenton oxidation unit electrolytic anodization to release ferrous iron ions, Depend on

Due to the circulation of the system, In order to prevent the generated ferrous iron ion catalyst from being oxidized to ferric iron by dissolved oxygen in the water body

ion, Turn on the power supply of the electrochemical oxidation tubular reactor some time in advance. The ferric ions can be reduced at the cathode to

Divalent iron ions ensure efficient electrocatalytic Fenton oxidation reaction.

[0030] Preferably,The number of cycles is three times in total. That is, the concentrated water generated by the reverse osmosis device for the first and
second times is recycled back to step S1 for processing. Finally, the concentrated water produced by the third reverse osmosis device is obtained, proceed to the next step

deal with.

[0031] Preferably,The current density of the electrochemical oxidation unit in step S2 is 5~25mA/cm2, preferably 8~
15mA/cm2. usually, As the current density gradually increases in the electrochemical oxidation step, The oxidation efficiency will be improved

trend,However, it was found in the present invention thatThe current density of the electrochemical oxidation step is between 8 and 15 mA/cm In the middle, 2 Fine Chemicals

The COD removal efficiency of tail water is relatively high.When increasing the current density,Its COD removal efficiency will decrease instead.and to a certain extent

As the current density increases, The COD removal rate shows a gradually decreasing trend. This is due to the fine chemical tailwater containing higher concentrations of

TDS, That is, the conductivity is higher, There are more ions in the system, When the current density increases, Electron transfer speeds up, ionic in the system

The more active the flow, theWhen too many ions are adsorbed on the cathode and anode surfaces due to the strong electric field, A "salt layer" will form covering the entire

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CN 111499056 A manual 4/10 pages

electrode surface,
This prevents the collision of pollutant molecules with the electrode surface. Reduced COD removal efficiency.

[0032] Preferably,The electrochemical oxidation time is 2 to 24 hours, Preferably it is 5 to 12 hours.

[0033] Preferably,In step S2, the electrocatalytic Fenton current density is 5~25mA/cm2, The preferred current density is 10~

25mA/cm2T;he electrolysis time is 2 to 12 hours. The preferred electrolysis time is 2 to 5 hours. Current density of electrocatalytic Fenton oxidation depends on wastewater

Depends on COD,
According to the ratio of ΔCOD to hydrogen peroxide 1: 0.5〜1, Fe2+The molar ratio to hydrogen peroxide is 1: 8〜20, Get the Fe you need 2+

concentration,
Then calculate the number of lost electrons according to Faraday's law, Finally, the actual required current is obtained. Under the above conditions, For COD
The concentration is 200~500mg/L,Fine chemical tailwater with TDS concentration of 4000~10000mg/L, Has high COD removal efficiency

Rate.
[0034] Preferably,In step S2, the electrocatalytic Fenton oxidation unit and the electrochemical oxidation unit are powered on for
40-120 minutes together.

[0035] Preferably,The fine chemical tail water contains TDS with a concentration greater than 500
[0036] The fine chemical tail water contains TDS at a concentration of 2,000 to 10,000 mg/L.
mg/L. Preferably,

[0037] Preferably,
After the water quality treated in step S2 reaches the reuse standard, Concentrated water treated by reverse osmosis device

Enter the evaporation device for evaporation,The salt obtained after evaporation undergoes mass fractionation and recrystallization.
By-products can be formed. This solution can be used

Reduce
To reduce the amount of evaporated water in the enterprise, evaporation costs,Improve the purity of the dry components after evaporation,Avoids direct evaporation of tail water

The resulting high COD in the salt after evaporation,The ingredients are complex,
The disadvantage is that it can only be treated as hazardousAt
waste.
the same time, it also avoids the large amount of water brought by

high evaporation costs.

[0038] 3. Beneficial effects

[0039] Compared with existing technology,

The beneficial effects of the present invention are:

[0040] (1) The present invention is aimed at the problem of low removal efficiency in the water reuse treatment process for fine chemical tailwater containing high salt.

question,
An electrochemical oxidation unit with a narrow channel connected in series with the electrocatalytic Fenton oxidation unit is provided, complex of iron ions
The anode breaks the complexes in the narrow channel electrochemical oxidation
at the
unit,same time, After
Since the distance between cathode and anode is small, that is, the breaking
channel is narrow,the iron ions,

Under the action of turbulence, it approaches the cathode and is reduced to ferrous ions at the cathode. Continue Fenton oxidation reaction,Therefore, the degradation efficiency of COD

The rate has been greatly improved;Further experiments found thatWhen the distance between cathode and anode is between 1 and 3 cm,
The COD removal rate is high;

[0041] But
(2) The management issues of RO membrane concentrated water reported in the current literature have gradually been paid attention to by the environmental due toindustry.
protection RO

Suspended
Membrane concentrated water contains a large amount of complex refractory organic matter, solids and high salt content, If treated by evaporation
hour, Often the color is higher,Resulting in the inability to become a by-product
Solid suspended matter, etc.,
This will cause high COD and high COD to remain in the salt obtained after evaporation.

products for recycling;The several-stage series "electrocatalytic Fenton oxidation-electrochemical oxidation + RO" combined process described in the
present invention, It can overcome the low treatment efficiency of electrochemical oxidation at low concentrations of pollutants. Disadvantages of high operating costs, Solve the problem

Traditional Fenton oxidation produces large amounts

Dealing
of mud,
with issues such as stagnation in efficiency,
Achieving refractory nitrogen-containing heterocycles in tail water from fine chemical production

Further reduction of organic matter, After the effluent is filtered through the RO membrane,
The RO membrane concentrated water continues to be returned to the "double oxidation"freshwater
process for treatment.

reuse; The double oxidation effluent continues to undergo RO treatment. fresh water for reuse;in this way
The membrane concentrated water is continued to be treated with "double oxidation".

A total of multi-stage "double oxidation" and RO processes are set up. Ultimately, COD was reduced from 300 to 500 mg/L to less than 60 mg/L.freshwater

TDS is processed from 2000~10000mg/L to below 100mg/L;

[0042] (3) In the present invention, in step S2,The electrocatalyst is turned on during the last period of electrolysis in the electrocatalytic Fenton oxidation unit.

Power supply for chemical oxidation units, Add H2O2Successor

After running for a specific time,Then turn off the power of the electrocatalytic Fenton oxidation unit,

Continue to run the electrochemical oxidation process, During the electrocatalytic Fenton oxidation unit electrolytic anodization to release ferrous iron ions,

Due to the circulatory flow of the system,In order to prevent the generated divalent iron ion catalyst from being oxidized to trivalent iron by dissolved oxygen in the water body,

iron ions,Turn on the power supply of the electrochemical oxidation tubular reactor some time in advance. Enable ferric ions to be reduced at the cathode

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CN 111499056 A manual Page 5/10

Ensure the efficient progress of the electrocatalytic Fenton oxidation reaction for divalent iron ions; Compared to the electrocatalytic Fenton electrolysis process at the end of

Turn on electrochemical oxidation, Starting electrochemical oxidation some time in advance will help further improve COD removal efficiency;

[0043] (4) The present invention is aimed at fine chemical tailwater containing high TDS concentration. The narrow channel electrochemical oxidation process used

The flow density is preferably 8 to 15 mA/cm2, Reduces the occurrence of iron side reactions,Able to maintain the COD removal efficiency of this type of tail water

higher level;
[0044] (5) The effluent after deep treatment by the combined process described in the present invention can achieve production process water reuse and

Circulating cooling water supplementary water, Water quality requirements for flushing toilets and flushing floors in the factory
Realized
area, the treatment of production wastewater from fine chemical enterprises

net zero emissions,

While protecting the environment, it also realizes the recycling of waste water. can bring long-term economic benefits,Has a wide range of

Value.

Description of the drawings

[0045] Figure 1 is a flow pattern diagram of a tubular membrane electrode in an electrochemical oxidation unit of the present invention; Figure 2 is a combined process flow chart for

[0046] reclaimed water reuse of fine chemical tailwater in Embodiment 1 of the present invention; Figure 3 is an embodiment of the present invention. 1 and Example 2 COD changes

[0047] over time under different electrochemical oxidation current densities in the primary treatment

Degradation efficiency chart;

[0048] Figure 4 shows the first level,Secondary and third-stage electro-Fenton/electrochemical double oxidation coupling devices with COD removal rates at any time

Degradation efficiency diagram (degradation efficiency calculated using the COD concentration before secondary/tertiary treatment as the starting concentration);

[0049] Figure 5 is a comparison chart of the COD degradation rate in Comparative Example 1A;

[0050] Figure 6 shows the 12h COD treated by the electrocatalytic Fenton oxidation process with different current densities in the primary treatment of Example 3.

removal rate;

[0051] Figure 7 is a comparison of COD removal rates in the primary treatment under different cathode and anode spacing conditions in the electrochemical oxidation tubular reactor in

Example 5.

Detailed ways
[0052] If no specific conditions are specified in the examples, Follow normal conditions or conditions recommended by the manufacturer. Reagents used

Or if the manufacturer is not indicated on the instrument, All are conventional products that can be purchased commercially.

[0053] current density,

Time and other numerical data can be presented in range format in this article. It should be understood that Such
The range format is used only for convenience and brevity, and should be flexibly interpreted to include not only
limit value,and also includes all individual values or subranges falling within the stated range, Just like each numerical sum

Subranges are explicitly stated as such. For example,Numerical ranges of about 1 to about 4.5 should be construed to include more than just the express recitation

a limit value of 1 to about 4.5,and also includes individual numbers (such as 2, 3,4) and subranges (such as 1 to 3, 2 to 4, etc.).

The same principle applies to describing a range of only one value, Something like "less than about 4.5", It should be construed to include all of the above

the stated values and ranges. also, Regardless of the scope or breadth of characteristics described, This interpretation should be applied.

[0054] The present invention will be further described below with reference to specific embodiments.

[0055] Figure 1 shows the flow pattern diagram of the tubular membrane electrode in the electrochemical oxidation unit. From left to right, there are yin and yang patterns

picture,
The anode uses a metal oxide tubular membrane electrode. The cathode is made of perforated stainless steel, graphite or titanium tubes. cathode and anode to

Parallel nested pattern assembly, The structure adopts "Flow-through" mode,The large internal view of the cathode and anode shown on the right side in Figure 1

Pollutant molecules enter with the water flow through the cathode perforation.Then collide with the anode surface, occur
As can be seen,Driven by external forces,

After the electrochemical oxidation reaction, it passes through the micropores on the anode surface. Finally, water is discharged from the outlet pipe at the top of the anode. This structure can significantly

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CN 111499056 A manual 6/10 pages

Increase the probability of collision between pollutants and anode surface, Enhance mass transfer efficiency,Further improve the degradation efficiency of pollutants.

[0056] An advanced treatment system for water reuse in fine chemical tail water according to the embodiment, Including three levels of hydrogen oxygen connected in series

chemical device, sedimentation tank and reverse osmosis device; The double oxidation device includes electrocatalytic Fenton oxidation units connected in sequence and interconnected.

element and narrow channel electrochemical oxidation unit. specifically, The double oxidation device includes a double oxidation reaction tank,High pressure pumps,
electrocatalytic fen

Dayton oxidation unit,Electrochemical oxidation unit,Intermediate pool, plate and frame filter press, Double oxidation reaction pool, intermediate pool and plate and frame pressure

The filters are all connected through circulation pipes.A high-pressure water pump is installed on the circulation pipe.
There is an outlet pipe at the bottom of the double oxidation reaction tank;Electric reminder

The anode of the Fenton oxidation unit is composed of a porous composite iron electrode (the preparation method is as described in the technical plan), The cathode uses

Hydrophobic material with strong reducing performance - modified graphite electrode, Use vacuum induction, sintering and other technologies to modify graphite electrodes

sex,A modified graphite electrode with strong reducing performance is produced.

New porous composite iron electrode for electro-Fenton oxidation device anode, compared to

traditional Fenton reaction, It has many active sites, Strong oxidizing ability,Advantages include low mud production.
[0057] The electrochemical oxidation device uses a microporous tubular membrane electrode of titanium matrix ruthenium dioxide as the anode and a titanium tube cathode. The

composition,
distance between the anode and cathode is 1 to 3 cm. The pore diameter of the titanium matrix ruthenium dioxide-coated microporous tubular membrane electrode is

10~50 microns. The inorganic tubular membrane electrode system in the electrochemical oxidation device of the present invention is improved on the basis of the traditional plate

electrochemical reactor. and use a titanium tube as the cathode to

Place the microporous tubular membrane electrode as the anode in the middle of the reactor.

surrounded,
Directional flow is generated by a high-pressure water pump. Organic pollutants in wastewater on the anode surface
Due to the accelerated mass transfer rate,

An instantaneous electrochemical oxidation reaction occurs on the ruthenium dioxide active layer,Nitrogen-containing heterocyclic compounds will open their rings to form small-molecule acids.

thereby being degraded.

[0058] When the fine chemical tailwater is running in the double oxidation device, First, turn on the electrocatalytic Fenton located in the double oxidation reaction tank.

The oxidation unit produces Fe by electrolysis2+, after a while,Turn on the power supply of the narrow channel electrochemical oxidation unit,After running for a specific time,
Then turn off the power of the electrocatalytic Fenton oxidation unit, Add H to the double oxidation reaction tank2O2, continue under electrochemical oxidation conditions

run, The fine chemical tailwater is circulated and oxidized for a period of time in the interconnected double oxidation reaction tank and the tubular narrow

channel electrochemical oxidation unit before entering the next step.

[0059] A treatment system for reclaimed water reuse of fine chemical tail water according to the present invention, Double processing by the above-mentioned level in turn

Oxidation device, inclined tube sedimentation tank, Pretreatment unit and reverse osmosis (RO) unit, Double oxidation device and inclined tube precipitation for secondary treatment

pool,
Pretreatment unit and reverse osmosis (RO) unit, Three-stage double oxidation device, inclined tube sedimentation tank, Pretreatment device and reaction

Osmosis (RO) device composition, Each device is connected through a connecting pipe equipped with a high-pressure water pump. Fine chemical tail water adjusted

After the pH reaches acidity, it enters the double oxidation device for treatment.
After the effluent settles in the inclined tube sedimentation tank, the effluent enters the intermediate Go
pool.
ahead

into a pretreatment device with filtration or filter press function, Then enter the first-level reverse osmosis device; Product water discharge of reverse osmosis device

Enter the produced water reuse pool, Such a cycle,Making progress together in the embodiment
The concentrated water returns to adjust the pH to acidity and then enters the double oxidation device for treatment.

Perform third-level processing.

[0060] The present invention uses high-flux titanium-based microfiltration tubular membrane electrodes.
And construct electrocatalytic Fenton/electrochemical double oxidation coupling

combined reaction system,Use double oxidation device to reduce COD first,Ensure the normal operation of the reverse osmosis (RO) device,
Solved the problem of reverse osmosis

(RO) Device stability issues.

[0061] Reverse osmosis technology is a reliable separation method, Based on a common phenomenon in nature - osmosis. Penetration is moisture

Diffusion through a semipermeable membrane. It penetrates from the high water molecule area (i.e. low concentration solution) into the low water molecule area (i.e. high

concentration Until
solution), while trapping salt and other elements in the water
the concentration inside and outside the cell is balanced (isotonic). The membrane allows water molecules to pass through,

until
components. The semipermeable membrane allows water molecules to penetrate from the low concentration side to the both
high sides reach
concentration side,the same salt concentration (osmotic level

balance). During the reverse osmosis process,Pressure acts on the concentrated water side to force water molecules to pass through the semipermeable membrane. Most dissolved salts, organic

things,
Bacteria and suspended solids cannot pass through the membrane.Drained together with system concentrate.

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CN 111499056 A manual Page 7/10

[0062] Example 1

[0063] Three-stage electrocatalytic Fenton/electrochemical double oxidation coupling device + reverse osmosis (RO) system combination process is used to treat three

Realize
Tailwater from the production of azoles nitrogen-containing heterocyclic compound the complete reuse of pesticide wastewater.
pesticides,

[0064] COD=500mg/L,TDS concentration is 4000mg/L.

The amount of water entering the tail water of pesticide production is 500m3/d，

[0065] A method for deep treatment of pesticide tailwater water reuse, as shown in picture 2:

[0066] step 1,at 500m Add sulfuric acid to the pesticide tail water, Adjust pH to 3.0~4.0;
3

[0067] Step 2.Electrocatalytic Fenton oxidation process: Pesticide tail water circulates in the double oxidation reaction tank, At the same time, electricity

Catalytic porous composite iron electrode to produce Fe2+, The electrocatalytic Fenton oxidation current density is 15mA/cm2, Reaction time up to 4h

hour,
Turn on the electrochemical oxidation unit (the operating conditions are the same as step 3), After running together for 1 hour,Shut down the electrocatalytic Fenton oxidation unit

Add 30% H to the system2O2,H2O2The dosage is 667kg/d.

power supply,

[0068] Step 3.Electrochemical oxidation process:Continue to run the electrochemical oxidation process;Between the cathode and anode of the electrochemical oxidation unit
The distance is 1cm,
The pore size of the titanium matrix ruthenium dioxide microporous tubular membrane electrode is 10 to 50 microns; The solution in the double oxidation reaction tank is

into the electrochemical oxidation unit, There is water inlet and outlet in the electrochemical oxidation tubular reactor. circulates between the double oxidation reaction tank and

The current density of the electrochemical oxidation unit is 10mA/cm2,The electrochemical oxidation unit continues to run for 7 hours (not included in the
complex,

1h) in the catalytic Fenton oxidation process. The process of step 2 and step 3 takes a total of 12 hours.The COD removal rate at different times is shown in Figure 3 (10mA/

cm2), The COD removal rate reaches more than 90% in 12h. Within the first 4 hours, Electrocatalytic Fenton unit anodic oxidation precipitation

ferrous iron ions,at the same time,Oxygen and hydrogen evolution reactions occur at the anode and cathode,The tiny gas formed by the generated hydrogen and oxygen

form scum,remove it,This part can contribute

The bubbles will wrap some of the suspended pollutants in the water and cause them to float to the surface of the system.

The formation of ferrous iron ions,After a series of hydrolysis,

COD removal;in addition, Polymerization and oxidation process of ferrous iron, develop into

Various hydroxyl complexes,Polynuclear hydroxyl complexes and even hydroxides,Colloidal impurities in wastewater, Suspended impurities agglomerate and settle

Charged pollutant particles swim in the electric field,

and separated;at the same time, Part of its charge is neutralized by the electrode, causing it to destabilize.

Shen. The above two methods can also contribute to COD removal. Also after the fourth hour, Turn on electrochemical oxidation, Electrochemical oxidation tube

The anodic oxidation of the formula electrode can also remove COD.

[0069] Step 4.The effluent treated in step 3 is treated in an inclined tube sedimentation tank.After treatment, the effluent is discharged into the intermediate pool;
[0070] Step 5. After the treatment in step 4, use a simple pre-treatment device of filtration or filter press to process and then enter the first level.

Reverse osmosis (RO) device;

[0071] Step 6. Use a reverse osmosis (RO) device to filter the pretreated water. Produced water (fresh water) COD of RO unit

The concentration is below 60mg/L, TDS is below 100mg/L,Discharge into the produced water reuse
Thepool,
amount of water produced after treatment by the RO device is approximately

325m3T,he volume of concentrated water is about

The175m
concentrated
, water continues to undergo advanced treatment;
3

[0072] Step 7. Continue to process the concentrated water in step 6 according to steps 1 to 5 (where, Second stage double oxidation device treatment

COD removal rate reaches 75% in 12h

The post-COD removal rate is shown in Figure 4, Calculation is based on the COD concentration before secondary treatment as the starting concentration.

above),The treated effluent enters the secondary reverse osmosis (RO) device;
[0073] Step 8. Use a reverse osmosis (RO) device to filter the effluent from step 7. The produced water from the RO unit is discharged into the produced water return

Use the pool,

The water production volume after treatment by the RO device is approximately 115mThe
3, amount of concentrated water is The
about
concentrated
60m3, water continues to undergo advanced treatment;

[0074] Step 9.Continue to process the concentrated water in step 8 according to steps 1 to 5 (where, COD in the third stage double oxidation treatment

COD removal rate reaches 60~70% in 12h

The removal rate is shown in Figure 4,Calculation is based on the COD concentration before the third-level treatment as the starting concentration.

above),The treated effluent enters the three-stage reverse osmosis (RO) device;
[0075] Step 10. Use a reverse osmosis (RO) device to filter the effluent from step 9. The produced water from the RO unit is discharged into the produced water return

Use the pool,

The water production volume after treatment by the RO device is approximately 40m
The
3, amount of concentrated water is about
The concentrated
20m3, water enters the evaporation device for evaporation.

9
CN 111499056 A manual 8/10 pages

Can be used
The salt obtained after evaporation undergoes mass fractionation and recrystallization. as a by-product.

[0076] Table 1 is a cost accounting table for pesticide tailwater treatment in Example 1. As can be seen from Table 1, Wastewater treatment costs mainly include two

part, liquid
They are pharmacy fees and electricity bills respectively. Pharmacy costs mainly come from hydrogen peroxide, alkali,
Chemical agents such as sulfuric acid; The electricity bill is mainly

It is generated by the DC power supply, high-pressure water pump, plate and frame filter press and other equipment in the device. After using a single

dropped
electrochemical oxidation to deeply process 500mg/LCOD, to below 60 mg/L,Using the same tubular membrane electrode as in the present invention, the

Water treatment capacity 500m3/d，

Perform electrochemical oxidation treatment, Current density is 10mA/cm2,The working voltage is 4V,The calculated electricity required

The flow is 235500A,The required time is 24h,The required electricity fee is 31.65 yuan/ton of water. The cost of this embodiment is only 4.31 yuan/

Compared with single electrochemical oxidation,The cost is greatly reduced.

tons of water,

[0077] Table 1 Summary of wastewater operation cost estimates

[0078]

[0079]

[0080] Note:
electricity bill,
The chemical fee is based on the water volume of 500 tons/day. Evaporation charges are based on 20 tons/day.

[0081] Comparative Example 1A

[0082] Carry out using basically the same conditions as in Example 1, Treating the same pesticide tailwater,The difference is that,
electrochemical oxygen

Treat the same pesticides

The chemical unit adopts a flat electrode with a cathode and anode spacing of 1 cm (the cathode and anode materials are the same as in Example 1),

tailwater;

[0083] Carry out using basically the same conditions as in Example 1, The difference is that,The electrochemical oxidation unit adopts a cathode-anode

Tubular membrane electrode with a distance of 8cm (the cathode and anode materials are the same as in Example 1), Treat the same pesticide tailwater;

[0084] In the above two cases, after first-level processing,secondary processing,Tertiary treatment,With the primary treatment in Example 1, two
level processing, Its COD degradation rate is shown in Figure 5.
Compared with the third-level treatment,

[0085] Comparing the removal rates of different forms of electrodes from primary to third-level treatment, it can be seen that Same cathode and anode spacing

case, Tubular membrane electrodes have better COD removal rates than flat electrodes. Mass transfer efficiency of flat plate electrodes and tubular membrane electrodes

There is a big gap compared to

Therefore, the degradation efficiency of pollutants is the lowest compared with tubular membrane electrodes. And between the tubular membrane electrodes

When the distance is wider (8cm),It was found that the removal efficiency was lower than that when the spacing (1cm) was narrower in Example 1, due toExplain the narrow channel pair

the degradation of pollutants and Fe2+The reduction effect is more obvious.

[0086] Example 2
[0087] In this example, it was investigated that when other conditions were basically the same as in Example 1, Only in the electrochemical oxidation step

Using different current densities: 5mA/cm28, mA/cm215mA/cm

, 2,20mA/cm2,25mA/cm2Conditional next-level processing (step 1

As shown in Figure 3,
to the COD removal efficiency of step 3) (only the COD removal efficiency of the double oxidation process of the primary treatment is examined), Current density

When the degree is low,The 12hCOD removal efficiency of pesticide tailwater is relatively low; Current density is 8~15mA/cm2hour, Pesticide tail water

The COD removal efficiency is higher, Its COD removal efficiency will decrease instead.and
When the current density is further increased, to a certain extent

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CN 111499056 A manual Page 9/10

As the current density increases,

The COD removal rate showed a gradually decreasing trend.

[0088] Example 3

[0089] Other conditions in this embodiment are basically the same as in Embodiment 1. The difference is,Only the first-level treatment of dual
COD removal efficiency in the oxidation process,The electrocatalytic Fenton oxidation current densities in the electrocatalytic Fenton oxidation process in step 2 are respectively

5mA/cm28, mA/cm21, 0mA/cm2,15mA/cm2,20mA/cm2,25mA/cm2,Other process conditions are the same, primary treatment

COD removal efficiency after (step 1 to step 3), As shown in Figure 6,In the 12 hours of "Electrocatalytic Fenton Oxidation-Electrochemical Oxidation"

middle,
When the electrocatalytic Fenton current density increases from 5 to 20mA/cm2During the process, COD removal rate continues to increase,
And when the current density

Continue to rise from 20 to 25mA/cm2hour,COD removal rate decreased slightly. This shows that when the Fe released in the system2+Concentration is one

within a certain range,Can promote Fenton reaction in the positive direction,And when Fe in the system2+As the concentration continues to rise,H2O2concentrated

Not enough H2O2Continue with excess Fe2+reaction,

The degree is certain, And
Causes Fenton reaction to slow down, excess Fe2+have
reduction,It will also increase the effluent COD.
[0090] Example 4

[0091] Other conditions in this embodiment are basically the same as in Embodiment 1. The difference is,Only the first-level treatment of dual
COD removal efficiency in the oxidation process, In step 2,The electrification time of electrocatalytic Fenton oxidation is 4 hours. Turn off the power and then add the
Enter H2O2(Not joining H2O2before turning on the electrochemical oxidation unit). Turn on the electrochemical oxidation unit in step 3,Run for 8h.
[0092] The 12h COD removal rate of double oxidation operation in primary treatment is approximately 81%. It can be seen from thisIn Example 1, the electrocatalyst
that

During the last period of Fenton oxidation, the electrochemical oxidation unit is turned on in advance. Both are carried out simultaneously,
Due to the circulation of the system

flow, The generated ferrous iron ion catalyst is oxidized to ferric iron ions by the dissolved oxygen in the water and reduced to ferrous iron ions at

the cathode. It can effectively ensure the efficient progress of electrocatalytic Fenton oxidation reaction.

[0093] Example 5

[0094] In this example, for the pesticide tail water that is basically the same as in Example 1, The same electrocatalytic Fenton/electrochemical dual

Oxidation coupling device and operating conditions, The difference is:Only the COD removal efficiency of the double oxidation process in the primary treatment is examined.
electricity

2, 3cm;The electrocatalytic Fenton oxidation current density is 20mA/cm ,

The distance between cathode and anode in the chemical oxidation unit is 1 respectively. 2 When powered on

The time is 5h, Turn on the electrochemical oxidation unit for 1 hour (electrochemical oxidation current density is 10mA/cm2),common
When the reaction time reaches 4 hours,

Turn off the power supply of the electrocatalytic Fenton oxidation unit,
After running for 1 hour, Add 30% H to the system2O2. With 10mA/cm2Current density
Continue to operate the electrochemical oxidation unit,
The energization time is 7 hours (excluding 1 hour in the energization time period of electrocatalytic Fenton oxidation). As

[0095] shown in Figure 7, It can be seen that as the distance between cathodes and anodes in the electrochemical oxidation tubular reactor expands from 1cm to 3cm,

COD removal rate decreased slightly,However, the overall COD removal rate can still reach more than 90%.This illustrates the narrow spacing between tubular reactors

(1〜3cm), For Fe3+-Cracking of organic carboxylic acid complexes and Fe2+The reduction has a positive promoting effect, make the coupling

The combined system can achieve continuous degradation of COD. A distance

1~3cm can be used as the preferred cathode and anode spacing. of 1cm is better.

[0096] Example 6

[0097] The three-stage electrocatalytic Fenton/electrochemical double oxidation coupling device + reverse osmosis (RO) system combination process is used to treat the anti-oxidant

Cancer drug intermediate production tail water, This tail water is production tail water containing 5-fluorouracil.

[0098] The amount of water entering the medical tail water is 500m3/d，COD=450mg/L,TDS concentration is 8000mg/L.
[0099] The difference is:Electrocatalytic Fenton oxidation current density is 10mA/cm2,
The processing steps are basically the same as in Example 1.

When the reaction time reaches 3.5h,Turn on the electrochemical oxidation unit, After running together for 1.5 hours,
Turn off the electricity of the electrocatalytic Fenton oxidation unit

Add
source, 30% H to the system2O2,H2O2The dosage is 500kg/d.
[0100] The COD removal rate of the primary treated double oxidation effluent after step 3 is 92%; the COD

[0101] removal rate of the secondary treated double oxidation effluent is 79%;

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CN 111499056 A manual 10/10 pages

[0102] The COD removal rate of the three-stage double oxidation effluent is 68%.

[0103] Example 7

[0104] Using a three-stage electrocatalytic Fenton/electrochemical double oxidation coupling device + reverse osmosis (RO) system combined process treatment

Industrial and new materials tail water,

The tail water is the production tail water of light stabilizer containing tetramethylpiperidinamine.

[0105] COD=400mg/L,TDS concentration is 7500mg/L.

The amount of water entering the tail water of new material production is 500m3/d，

[0106] The processing steps are basically the same as in Example 1.The difference is:Electrocatalytic Fenton oxidation current density is 10mA/cm2,
When the reaction time reaches 3 hours,Turn on the electrochemical oxidation unit,
After running together for 1.5 hours,Turn off the electricity of the electrocatalytic Fenton oxidation unit

Add
source, 30% H to the system2O2,H2O2The dosage is 467kg/d.
[0107] After step 3, the COD removal rate of the primary treated double oxidation effluent is 89%; the COD

[0108] removal rate of the secondary treated double oxidation effluent is 78%;

[0109] The COD removal rate of the three-stage double oxidation effluent is 69%.

[0110] The above content is a schematic description of the present invention and its implementation. This description is not limiting,Reality

What is shown in the examples or drawings is only one embodiment of the present invention. The reality is not limited to this. so, If this field
Ordinary technicians were inspired by it,Without departing from the spirit of the present invention,Designed without creativity to match the

Similar structural methods and embodiments of technical solutions, All should fall within the protection scope of the present invention.

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CN 111499056 A Instructions with pictures 1/4 page

figure 1

figure 2

13
CN 111499056 A Instructions with pictures 2/4 pages

image 3

Figure 4

14
CN 111499056 A Instructions with pictures 3/4 pages

Figure 5

Figure 6

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CN 111499056 A Instructions with pictures 4/4 pages

Figure 7

16