CN108773978A - A kind of organic silicon wastewater processing system and its processing method - Google Patents
A kind of organic silicon wastewater processing system and its processing method Download PDFInfo
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Abstract
The present invention provides a kind of organic silicon wastewater processing system and its processing methods.The system comprises sequentially connected waste water pretreatment system and waste water treatment system, the waste water treatment system includes that sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, heating unit, catalytic wet oxidation unit, gas-water separation unit and biochemical treatment unit.It the treating method comprises and organic silicon wastewater is pre-processed, after carrying out neutralization adjusting, inorganic ions precipitation, heating, catalytic wet oxidation, gas-water separation and biochemical treatment successively to obtained pretreated organic silicon wastewater, obtain waste water up to standard.System process provided by the invention is simple, avoid the use of multi-stage oxidizing, and continuous operation, greatly reduce occupation area of equipment, and there is good compatibility, a variety of silicones that complicated component, type are various, biodegradability is poor, silicon rubber waste water can be made to be effectively addressed in same system.
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of organic silicon wastewater processing system and its processing method.
Background technology
Organosilicon material have high-low temperature resistant, weather-proof, electric insulation, radiation hardness, fire-retardant, corrosion-resistant, physiological inertia and
The good characteristics such as biocompatibility, thus be widely used in aerospace, defence and military, electronic apparatus, oil, light industry, building,
The fields such as metallurgy, machinery, office equipment, communications and transportation, food processing, daily-use chemical industry, are known as the title of " industrial monosodium glutamate ", product
It can be divided mainly into silicone oil, four major class of silicon rubber, silicones and silane coupling agent.
Silicones is domestic at present to be mainly made using siloxanes Hydrolyze method, and a large amount of high containing alcohol and silicon are generated in production process
Resin oligomers waste water.Silicon rubber generates a certain amount of waste water containing a large amount of organosilicon low molecules and alcohols in process of production,
107 raw rubbers and 110 raw rubbers also will produce a small amount of low molecular waste water containing organosilicon in process of production.Silicones, silicon rubber
Waste water has the characteristics that type is complicated, biodegradability is poor, discharge of wastewater fluctuation is big, regularity is poor, perplexs organosilicon all the time
The development in downstream.At present both at home and abroad main treatment technology have " iron filings fluid bed+Fenton catalysis oxidations+coagulation ", " stripping+
Acidification+light electrolysis+aeration+coagulation ", " oil removal+air supporting+coagulation+sand filtration " etc..Traditional treatment method have sludge yield it is big,
Place occupancy is big, treatment process is complicated, is difficult to handle waste water complicated and changeable, and processed waste water index is difficult to reach national row
Put numerous deficiencies such as requirement.
105347612 A of CN disclose a kind of purifying treatment method containing organic silicon wastewater, and organic silicon wastewater passes through successively
Cross anaerobic reaction, aerobic reaction, flocculation sediment, secondary anaerobic reaction, secondary aerobic reaction and the processing of secondary flocculation sediment, the party
Method can directly be handled the COD containing organic silicon wastewater to 50mg/L or less.But this method is only applicable to CODcr≤3500mg/
L, it is complicated and high can not to handle the type generated in organosilicon downstream product production process for the system of chlorion≤4000mg/L
The organic silicon waste water of COD.
105293807 A of CN disclose a kind of organic silicon wastewater cleaning treatment system, including pipeline is used to be sequentially connected in series
Flocculation sediment device, stripper, catalytic oxidizer, active carbon filter and reuse water tank, by being carried out successively to organic silicon wastewater
Flocculation, stripping, catalysis oxidation and filtration treatment and by organic silicon wastewater Recovery Purifying, reach the discharge standard of national regulation, but
The system need to use stripping and catalysis oxidation, and there are required equipment cost height, and energy consumption is higher, and pharmaceutical use is big and dirty
The shortcomings of mud yield is big.
102976537 B of CN disclose a kind of the synthesis apparatus for physical Chemical treating and method of organic silicon wastewater, and waste water is through toning
Save pond pretreatment, first time micro-filtration rotation membrane filtration, the irradiation of first time ultraviolet light, first time Inner electrolysis, second of micro-filtration rotation
Membrane filtration, second of ultraviolet light irradiation, second of Inner electrolysis, third time micro-filtration rotation membrane filtration, activated carbon adsorption, carbon mineral wool
It polymerize pellet absorption and ultra filtering reverse osmosis filtering, water outlet is made to reach national grade one discharge standard.Ultraviolet irradiation involved in this method,
The techniques such as Inner electrolysis, equipment investment is big, high energy consumption；It is related to the devices such as microfiltration membranes, reverse osmosis membrane, film its processing in use
Amount can be gradually reduced, and discarded film generates pollution to environment.
104291509 B of CN disclose a kind of the classification processing unit and method of organic silicon wastewater, the processing unit packet
Primary wastewater processing unit, secondary waste water processing unit, three-level treatment unit for waste water and level Four treatment unit for waste water are included, it is right respectively
A kind of waste water, two class waste water, three classes waste water and four class waste water are handled accordingly, are then directed to further according to the characteristics of waste water
The carry out wastewater treatment of property.Vapo(u)rization system, light electrolysis system, advanced oxidation system, UASB systems, contact oxygen involved in this method
Numerous processing systems such as change system, complex treatment process take up a large area, and processing cost is high, sludge yield is big.
Therefore, how the organic silicon wastewater that processes composition is complicated, type is various, biodegradability is poor, to obtain waste water up to standard；
It avoids chemical sludge to generate simultaneously, simplifies treatment process, reduces floor space, be problem to be solved.
Invention content
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of organic silicon wastewater processing systems
System and its processing method.Processing system and processing method provided by the invention can make different types of silicones, silicon rubber production
Waste water reach after processing waste water national grade one discharge standard (《Integrated wastewater discharge standard》GB8978-1996).
For this purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of organic silicon wastewater processing system, the system comprises sequentially connected waste water
Pretreatment system and waste water treatment system, the waste water treatment system include that sequentially connected neutralization adjusts unit, inorganic ions
Precipitation unit, heating unit, catalytic wet oxidation unit, gas-water separation unit and biochemical treatment unit.
In the present invention, the system is referred to as device, equipment or process units and its combination etc..
Organic silicon wastewater processing system provided by the invention can make that complicated component, type are various, biodegradability is poor, rule
Property difference a variety of silicones, silicon rubber waste water be effectively addressed in same system, system have good compatibility, system
Water outlet reaches discharge standard.
In the present invention, waste water can be carried out under the conditions of the temperature and pressure of milder by catalytic wet oxidation unit
Oxidation processes, the system for simplifying processing have saved energy consumption and cost, and by the selection of suitable catalyst, can
More efficiently to handle sewage.And in the system of the present invention, each unit in waste water treatment system cooperates,
Collective effect so that organic silicon wastewater processing system provided by the invention can make different types of silicones, silicon rubber production useless
Water reaches waste water national grade one discharge standard after processing.
System provided by the invention has good compatibility, and it is a variety of to make that complicated component, type are various, biodegradability is poor
Silicones, silicon rubber waste water are effectively addressed in same system.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the waste water pretreatment system includes silicones waste water pretreatment system
And/or silicon rubber waste water pretreatment system.The silicones waste water pretreatment system and/or silicon rubber waste water pretreatment system are
Finger can be silicones waste water pretreatment system, or silicon rubber waste water pretreatment system can also be silicones waste water
Pretreatment system and silicon rubber waste water pretreatment system.
Preferably, the silicones waste water pretreatment system includes rectifier unit.
Preferably, the rectifier unit includes rectifying column.
Preferably, the silicon rubber waste water pretreatment system includes oil-isolating device or air-floating apparatus.
Preferably, the silicones waste water is the organic silicon wastewater that alcohol content is 2%~70%, for example, alcohol content be 2%,
5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70% etc., but simultaneously
It is not limited only to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.Here alcohol content is quality
Content, i.e. mass fraction.
Preferably, the silicon rubber waste water is the organic silicon wastewater that organosilicon low molecule content is 1%~40%, such as is had
Machine silicon low molecule content is 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40% etc., it is not limited to institute
The numerical value enumerated, other interior unrequited numerical value of the numberical range are equally applicable.Here organosilicon low molecule content is quality
Content, i.e. mass fraction.
Preferably, the organosilicon low molecule is the organic silicon molecule of molecular weight < 1000, such as organic silicon molecule
Molecular weight be 999,900,800,750,700,650,600,500,450,300,150 or 100 etc..
As currently preferred technical solution, the organic silicon wastewater is silicones waste water and/or silicon rubber waste water.Institute
State silicones waste water and/or silicon rubber waste water refer to can be silicones waste water, or silicon rubber waste water can also be silicon
The combination of resin wastewater and silicon rubber waste water.
Preferably, the heating unit includes sequentially connected heat exchanger and preheater.
As currently preferred technical solution, the catalytic wet oxidation unit includes catalytic wet oxidation device.
Preferably, the catalytic wet oxidation device is fixed bed reactors.
Preferably, built-in load type metal catalyst in the catalytic wet oxidation device.In the waste water that the present invention is handled
In system, it can avoid silicones, silicon rubber performed polymer in oxidation process waste water using this catalyst and be further condensed, lead
It causes silicones, silicon rubber that reaction generates to cover catalyst surface reactivity site, leads to catalyst inactivation.
Preferably, the carrier of the load type metal catalyst is ceramic-absorbent charcoal, Al2O3Activated carbon, TiO2Activity
Charcoal or SiO2In activated carbon any one or at least two combination, it is typical but be non-limiting combination and have：Ceramics-are living
Property charcoal and Al2O3The combination of activated carbon, Al2O3Activated carbon and TiO2The combination of activated carbon, TiO2Activated carbon and SiO2Activity
The combination etc. of charcoal.
Preferably, the Al2O3Al in activated carbon2O3For γ-Al2O3。
Load type metal catalyst in the present invention using this composite carrier be both utilized activated carbon can provide it is abundant
Internal surface of hole, unsaturated valence and defective bit, the gap structure of prosperity, huge specific surface area, excellent absorption property etc. it is excellent
Point also takes full advantage of ceramics, γ-Al2O3、TiO2、SiO2The excellent mechanical performance such as equal materials high temperature high voltage resistant, wear-resistant
With the physical properties such as high absorption, high-specific surface area, so that them is cooperateed with mutually, reach better effect.
Preferably, the metal catalytic activity substance of the load type metal catalyst be Cu, Fe, Ni, Mn, Pt, Ir, Pd,
In Rh or Ru any one or at least two combination, it is typical but be non-limiting combination and have：The combination of Cu and Fe, Fe and
The combination of the combination of the combination of Ni, Ni and Mn, Pt and Ir, the combination etc. of Pd, Rh and Ru.In the present invention, above-mentioned preferred metal is former
At least one position of out orbit of son is empty, and the surface of metallic atom is " exposed ", utilizes metal surface
The activation energy generated in organic matter and oxygen reaction process needed for hydroxyl radical free radical can be greatly lowered in metastable condition, and then drops
Temperature and pressure needed for low wet oxidation.
As currently preferred technical solution, gas vent and the air governing system phase of the gas-water separation unit
Even.
Preferably, the biochemical treatment unit includes aerobic oxidation device.
Preferably, built-in aerobic bacteria in the aerobic oxidation device.Aerobic bacteria of the present invention is that this field is conventional
Bacterium, specific type those skilled in the art according to circumstances can voluntarily choose.
Second aspect, the present invention provide a kind of processing method of the processing system of organic silicon wastewater as described in relation to the first aspect, institute
The method of stating includes the following steps：
Organic silicon wastewater is pre-processed, to obtained pretreated organic silicon wastewater carry out successively neutralization adjusting,
After inorganic ions precipitation, heating, catalytic wet oxidation, gas-water separation and biochemical treatment, waste water up to standard is obtained.
In the processing method provided by the present invention, each step is mutually to cooperate with, and is worked in coordination, and realizes reaching for waste water jointly
Mark discharge.In the processing method provided by the present invention, organic silicon wastewater is pre-processed first so that the alcohol in silicones waste water
It is recycled utilization with the low molecule in silicon rubber waste water, the waste of resource is avoided, reduces catalytic wet oxidation and biochemistry
The processing load of system；Then it carries out neutralizing and adjusts pH, carry out inorganic ions precipitation and remove Ca2+、Mg2+、Cu2+Deng easily heavy
The ion in shallow lake, carrying out heating makes waste water reach the temperature needed for catalytic wet oxidation, then carries out catalytic wet oxidation and removes greatly
Part debirs reduce COD (Chemical Oxygen Demand, COD), and gas-water separation is recycled to remove not
The gaseous oxidant of reaction obtains waste water up to standard finally after biochemical treatment.
Wherein, catalytic wet oxidation simplifies the processing technological flow of the present invention, avoids the use of multi-stage oxidizing, and can
Continuous operation greatly reduces occupation area of equipment, does not have NO in oxidation processx、SO2, the harmful substances such as HCl, CO production
Raw, secondary pollution is small, consuming little energy, and recoverable energy and useful material, and processing system pharmaceutical use is few for this, does not generate
Chemical sludge greatly reduces dangerous waste processing cost.
As currently preferred technical solution, the pretreatment is silicones Wastewater Pretreatment and/or silicon rubber waste water
Pretreatment.The silicones Wastewater Pretreatment and/or silicon rubber Wastewater Pretreatment refer to can be silicones Wastewater Pretreatment,
It can be silicon rubber Wastewater Pretreatment, can also be the combination of silicones Wastewater Pretreatment and silicon rubber Wastewater Pretreatment.
Preferably, the silicones Wastewater Pretreatment includes：Rectification process is carried out to silicones waste water under alkaline condition.
Rectifying can not only remove the alcohols in waste water under alkaline condition, can also make the unreacted silicones performed polymer in waste water further
Condensation reaction occurs and generates silicones, the silicone resin component in waste water is reduced, to reduce the intractability of waste water.
Preferably, the pH of the alkaline condition be 8.0~12.0, such as 8.0,8.5,9.0,9.5,10.0,10.5,
11.0,11.5 or 12.0 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With.
Preferably, the silicones waste water is after pretreatment, and dichromate oxidizability (CODcr) in waste water≤
30000mg/L and alcohols≤1wt%.
Preferably, the silicon rubber Wastewater Pretreatment includes：Silicon rubber waste water is handled through oil removal or air-dissolving air-float.
Preferably, the silicon rubber waste water is after pretreatment, dichromate oxidizability≤40000mg/L and organosilicon is low
Molecule≤1wt%.
Preferably, the organosilicon low molecule is the organic silicon molecule of molecular weight < 1000, such as organic silicon molecule
Molecular weight be 999,900,800,750,700,650,600,500,450,300,150 or 100 etc..
Preferably, the organic silicon wastewater is silicones waste water and/or silicon rubber waste water.The silicones waste water and/or
Silicon rubber waste water refer to can be silicones waste water, or silicon rubber waste water can also be silicones waste water and silicon rubber
The combination of waste water.
As currently preferred technical solution, the neutralization adjusts the pH value of waste water being adjusted to 6~10, such as 6,7,
8,9 or 10 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the temperature of inorganic ions precipitation is 60~100 DEG C, such as 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100
DEG C etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the residence time of the inorganic ions precipitation is 0.5~1.5h, such as 0.5h, 0.75h, 1h, 1.25h
Or 1.5h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the heating includes that heat exchanger heats and warming up device heating.
Preferably, waste liquid is heated to 120~150 DEG C by heat exchanger heating, for example, 120 DEG C, 125 DEG C, 130 DEG C, 140
DEG C, 145 DEG C or 150 DEG C etc., it is not limited to cited numerical value, other unrequited numerical value are equally suitable in the numberical range
With.
Preferably, the heat exchanger uses the processed waste water of catalytic wet oxidation as heat source.
Preferably, waste liquid is heated to 150~300 DEG C by preheater heating, for example, 150 DEG C, 160 DEG C, 170 DEG C, 180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C or 300 DEG C
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the oxidant of the catalytic wet oxidation is air and/or oxygen, the preferably group of air and oxygen
It closes.Here, the air and/or oxygen refer to can be air, or oxygen, can also be air and oxygen group
It closes.
Preferably, the catalyst of the catalytic wet oxidation is load type metal catalyst.
Preferably, the carrier of the load type metal catalyst is ceramic-absorbent charcoal, Al2O3Activated carbon, TiO2Activity
Charcoal or SiO2In activated carbon any one or at least two combination, it is typical but be non-limiting combination and have：Ceramics-are living
Property charcoal and Al2O3The combination of activated carbon, Al2O3Activated carbon and TiO2The combination of activated carbon, TiO2Activated carbon and SiO2Activity
The combination etc. of charcoal.
Preferably, the Al2O3Al in activated carbon2O3For γ-Al2O3。
Load type metal catalyst in the present invention using this composite carrier be both utilized activated carbon can provide it is abundant
Internal surface of hole, unsaturated valence and defective bit, the gap structure of prosperity, huge specific surface area, excellent absorption property etc. it is excellent
Point also takes full advantage of ceramics, γ-Al2O3、TiO2、SiO2The excellent mechanical performance such as equal materials high temperature high voltage resistant, wear-resistant
With the physical properties such as high absorption, high-specific surface area, so that them is cooperateed with mutually, reach better effect.
Preferably, the metal catalytic activity substance of the load type metal catalyst be Cu, Fe, Ni, Mn, Pt, Ir, Pd,
In Rh or Ru any one or at least two combination, it is typical but be non-limiting combination and have：The combination of Cu and Fe, Fe and
The combination of the combination of the combination of Ni, Ni and Mn, Pt and Ir, the combination etc. of Pd, Rh and Ru.In the present invention, above-mentioned preferred metal is former
At least one position of out orbit of son is empty, and the surface of metallic atom is " exposed ", utilizes metal surface
The activation energy generated in organic matter and oxygen reaction process needed for hydroxyl radical free radical can be greatly lowered in metastable condition, and then drops
Temperature and pressure needed for low wet oxidation.
Preferably, the reaction temperature of the catalytic wet oxidation be 150~300 DEG C, such as 150 DEG C, 170 DEG C, 190 DEG C,
200 DEG C, 220 DEG C, 240 DEG C, 260 DEG C, 280 DEG C or 300 DEG C etc., it is not limited to cited numerical value, in the numberical range
Other unrequited numerical value are equally applicable.
Preferably, the reaction pressure of the catalytic wet oxidation be 0.5~12MPa, such as 0.5MPa, 1MPa, 2MPa,
4MPa, 6MPa, 8MPa, 10MPa or 12MPa etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value it is equally applicable.
Preferably, in the reaction system of the catalytic wet oxidation, oxygen partial pressure be 0.5~5.0MPa, such as 0.5MPa,
1MPa, 2MPa, 3MPa, 4MPa or 5MPa etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable.
Preferably, the waste liquid Feed space velocities of the catalytic wet oxidation are 0.2~2h-1, such as 0.2h-1、0.5h-1、1h-1、
1.5h-1Or 2h-1Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
As currently preferred technical solution, liquid phase that the gas-water separation generates carries out subsequent again after condensation
Biochemical treatment.
Preferably, the gas phase that the gas-water separation generates enters air governing system.
Preferably, the dichromate oxidizability for the liquid phase that the gas-water separation generates is 100~1000mg/L.
Preferably, the biochemical treatment is to carry out aerobic oxidation processing using aerobic bacteria.
Preferably, the processing time of the biochemical treatment is 10~20h, such as 10h, 12h, 14h, 16h, 18h or 20h
Deng it is not limited to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, the inflow temperature of the biochemical treatment be 20~40 DEG C, such as 20 DEG C, 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C,
30 DEG C, 32 DEG C, 34 DEG C, 36 DEG C, 38 DEG C or 40 DEG C etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.
Preferably, the inlet flow-patterm of the biochemical treatment is 6~9, such as 6,7,8 or 9 etc., it is not limited to cited
Numerical value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the dichromate oxidizability of the waste water up to standard is≤50mg/L, pH=6.0~9.0.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
Silicones Wastewater Pretreatment and/or silicon rubber Wastewater Pretreatment, the pretreatment to obtaining are carried out to organic silicon wastewater
Organic silicon wastewater afterwards carries out neutralizing adjusting successively by the pH value of waste water is adjusted to 6~10, carried out at 60~100 DEG C it is inorganic from
The residence time of son precipitation, inorganic ions precipitation is 0.5~1.5h, carry out later heat exchanger heating waste liquid is heated to 120~
150 DEG C, waste liquid is heated to 150~300 DEG C by preheater heating, then under 150~300 DEG C and 0.5~12MPa, with air
Combination with oxygen is 0.2~2h to Feed space velocities with load type metal catalyst as oxidant-1Waste water carries out catalytic wet
Oxidation, then carries out gas-water separation, to being carried out under conditions of 20~40 DEG C of temperature and 6~9 pH after obtained liquid phase condensate
The time of aerobic bacteria biochemical treatment, biochemical treatment is 10~20h, obtains waste water up to standard；
Wherein, the silicones Wastewater Pretreatment is that rectification process is carried out at 8.0~12.0 pH, and the silicon rubber is useless
Water pretreatment is to be handled through oil removal or air-dissolving air-float silicon rubber waste water；The carrier of the load type metal catalyst is ceramics-
Activated carbon, γ-Al2O3Activated carbon, TiO2Activated carbon or SiO2Any one in activated carbon；The load type metal catalysis
The metal catalytic activity substance of agent is the group of any one or at least two in Cu, Fe, Ni, Mn, Pt, Ir, Pd, Rh or Ru
It closes；In the reaction system of the catalytic wet oxidation, oxygen partial pressure is 0.5~5.0MPa.
Compared with prior art, the invention has the advantages that：
(1) organic silicon wastewater processing system technological process provided by the invention is simple, avoids the use of multi-stage oxidizing, and
Continuous operation greatly reduces occupation area of equipment；The organic silicon wastewater processing system has good compatibility, can make
Complicated component, type are various, biodegradability is poor a variety of silicones, silicon rubber waste water are effectively addressed in same system；
(2) processing method of organic silicon wastewater processing system provided by the invention is made by pretreatment in silicones waste water
Alcohol and silicon rubber waste water in low molecule be recycled utilization, avoid the waste of resource, reduce wet oxidation and biochemistry
The processing load of system；
(3) processing method of organic silicon wastewater processing system provided by the invention is synchronous with alkaline hydrolysis by silicones waste water rectifying
It carries out, the alcohols in waste water can be not only removed in distillation process, can also make unreacted silicones performed polymer in waste water into one
Step occurs condensation reaction and generates silicones, reduces wastewater treatment difficulty；
(4) in the processing method of organic silicon wastewater processing system provided by the invention, do not have during catalytic wet oxidation
NOx、SO2, the harmful substances such as HCl, CO generation, waste water air speed is big, up to 2h-1, secondary pollution is small, consuming little energy, and can
It recovers energy and useful material, processing system pharmaceutical use is few for this, does not generate chemical sludge, greatly reduces dangerous waste handling
With；
(5) the usable solid heterogeneous catalyst of the present invention avoids homogeneous catalyst economic damage caused by due to loss
Mistake and the secondary pollution to environment, reduce the temperature and pressure needed for catalysis oxidation, greatly reduce equipment investment；The present invention
The loaded catalyst used can effectively avoid the further condensation of silicones in catalytic oxidation process, silicon rubber performed polymer, keep away
Exempt from active catalyst sites to cover, leads to catalyst inactivation.
Description of the drawings
Fig. 1 is the process flow chart for the organic silicon wastewater processing system that the embodiment of the present invention 1 provides；
Fig. 2 is the process flow chart for the organic silicon wastewater processing system that the embodiment of the present invention 2 provides；
Fig. 3 is the process flow chart for the organic silicon wastewater processing system that the embodiment of the present invention 3 provides.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
It is present invention typical case but non-limiting embodiment below：
Embodiment 1
The organic silicon wastewater processing system of the present embodiment includes sequentially connected waste water pretreatment system and wastewater treatment system
System, the waste water pretreatment system includes silicones waste water pretreatment system (rectification cell), and the waste water treatment system includes
Sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, heating unit (heat exchange and preheating unit), catalytic wet oxidation
Unit, gas-water separation unit and biochemical treatment unit.The process flow chart of organic silicon wastewater processing system provided in this embodiment
As shown in Figure 1.
Its processing method includes the following steps：
1) it by the silicones microballoon waste water 8000Kg that methanol content is 15%, CODcr 230000mg/L, pH are 9, is added
5Kg sodium hydroxides, it is 10.5 to adjust pH, controls reflux ratio 1:Under the conditions of 1, rectifying to bottom temperature is 100~102 DEG C, tower top
Temperature is 65~72 DEG C, and recovered overhead methanol content is more than 99.5%, and tower bottoms CODcr is 10000mg/L, and methanol content is
0.5%；
2) the rectifying tower kettle liquid concentrated sulfuric acid is adjusted into pH to 7.0~8.0, waste water adjusts the temperature to 90~100 DEG C, stops
Time is 0.5h, through inorganic ions settling step, removes easy precipitating ion in waste water；
3) waste-heat is discharged to 150 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 200 DEG C；
4) waste water after heat exchange and the pre-heat treatment is with 1.0h-1Liquid air speed enter catalytic wet oxidation system, it is used negative
Supported catalyst carrier is ceramic-absorbent charcoal, and active component is metal Ru, and reaction temperature is 200~220 DEG C, while passing through sky
It is 10MPa, oxygen partial pressure 0.5MPa that air compressor, which controls reaction pressure,；
5) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 30~35 DEG C after residual heat recovery and condensation, and surveyed catalytic wet oxidation effluent index is COD
For 100mg/L；
6) waste water after gas-liquid separation enters biochemical system, residence time 12h.Bio-chemical effluent index is that CODcr is
20mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Embodiment 2
The organic silicon wastewater processing system of the present embodiment includes sequentially connected waste water pretreatment system and wastewater treatment system
System, the waste water pretreatment system includes silicon rubber waste water pretreatment system (oil removal unit), and the waste water treatment system includes
Sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, heating unit (heat exchange and preheating unit), catalytic wet oxidation
Unit, gas-water separation unit and biochemical treatment unit.The process flow chart of organic silicon wastewater processing system provided in this embodiment
As shown in Figure 2.
Its processing method includes the following steps：
1) by rubber compound waste water 8000Kg after oil-isolating device is handled, the low molecule in rubber compound waste water, low molecule are removed
It is back to the production of 107 raw rubbers, waste water index is that CODcr is 15000mg/L, ethanol content 0.6%, pH value 8.
2) glue layer will be kneaded and adjusts pH to 7.0~8.0, waste water adjusts the temperature to 60~70 DEG C, residence time 1.0h,
Through inorganic ions settling step, easy precipitating ion in waste water is removed；
3) waste-heat is discharged to 140 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 180 DEG C；
4) waste water after heat exchange and the pre-heat treatment is with 1.5.0h-1Liquid air speed enter catalytic wet oxidation system, it is used
Supported catalyst agent carrier is γ-Al2O3Activated carbon, active component are metal Pd and Ir, and reaction temperature is 180~200 DEG C, together
When to control reaction pressure by air compressor and oxygen bottle be 8MPa, oxygen partial pressure 0.5MPa；
5) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 30~35 DEG C after residual heat recovery and condensation, and surveyed catalytic wet oxidation effluent index is COD
For 200mg/L；
6) waste water after gas-liquid separation enters biochemical system, residence time 20h.Bio-chemical effluent index is that CODcr is
37mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Embodiment 3
The organic silicon wastewater processing system of the present embodiment includes sequentially connected waste water pretreatment system and wastewater treatment system
System, the waste water pretreatment system includes silicones waste water pretreatment system (rectifier unit) and silicon rubber waste water pretreatment system
(dissolved air flotation device), the waste water treatment system include that sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, adds
Hot cell (heat exchange and preheating unit), catalytic wet oxidation unit, gas-water separation unit and biochemical treatment unit.The present embodiment carries
The process flow chart of the organic silicon wastewater processing system of confession is as shown in Figure 3.
Its processing method includes the following steps：
1) by rubber compound waste water 8000Kg after dissolved air flotation device oil removing, the low molecule in rubber compound waste water is removed, it is low
Molecule is back to the production of 107 raw rubbers, and waste water index is that CODcr is 20000mg/L, ethanol content 0.9%, pH value 7.5.
2) it by the silicones microballoon waste water 8000Kg that methanol content is 20%, CODcr 260000mg/L, pH are 9, is added
3Kg sodium hydroxides, it is 10.0 to adjust pH, controls reflux ratio 1:Under the conditions of 1, rectifying to bottom temperature is 100~102 DEG C, tower top
Temperature is 65~72 DEG C, and recovered overhead methanol content is more than 99.5%, and tower bottoms CODcr is 8000mg/L, and methanol content is
0.8%；
3) pH to 7.0~8.0 will be adjusted after glue layer and the mixing of rectifying column kettle liquid will be kneaded, waste water adjusts the temperature to 70~75
DEG C, residence time 1.0h removes easy precipitating ion in waste water through inorganic ions settling step；
4) waste-heat is discharged to 150 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 250 DEG C；
5) waste water after heat exchange and the pre-heat treatment is with 2.0h-1Liquid air speed enter catalytic wet oxidation system, it is used negative
Supported catalyst carrier is TiO2Activated carbon, active component be Ni metal, Ru and Ni threes mixture, reaction temperature 250
~270 DEG C, while it is 12MPa, oxygen partial pressure 1.5MPa to control reaction pressure by air compressor and oxygen bottle；
6) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 20~25 DEG C after residual heat recovery and condensation, and surveyed catalytic wet oxidation effluent index is COD
For 150mg/L；
7) waste water after gas-liquid separation enters biochemical system, residence time 20h.Bio-chemical effluent index is that CODcr is
28mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Embodiment 4
The organic silicon wastewater processing system of the present embodiment is same as Example 3.
Its processing method includes the following steps：
1) by rubber compound waste water 8000Kg after dissolved air flotation device oil removing, the low molecule in rubber compound waste water is removed, it is low
Molecule is back to the production of 107 raw rubbers, and waste water index is that CODcr is 20000mg/L, ethanol content 0.9%, pH value 7.5.
2) it by the silicones microballoon waste water 8000Kg that methanol content is 20%, CODcr 260000mg/L, pH are 9, is added
Sodium hydroxide, it is 8 to adjust pH, controls reflux ratio 1:Under the conditions of 1, rectifying to bottom temperature is 100~102 DEG C, and tower top temperature is
65~72 DEG C, recovered overhead methanol content is more than 99.5%, and tower bottoms CODcr is 8000mg/L, methanol content 0.8%；
3) pH to 6.0~7.0 will be adjusted after glue layer and the mixing of rectifying column kettle liquid will be kneaded, waste water adjusts the temperature to 70~75
DEG C, residence time 1.5h removes easy precipitating ion in waste water through inorganic ions settling step；
4) waste-heat is discharged to 120 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 150 DEG C；
5) waste water after heat exchange and the pre-heat treatment is with 0.2h-1Liquid air speed enter catalytic wet oxidation system, it is used negative
Supported catalyst carrier is TiO2Activated carbon, active component be Ni metal, Ru and Ni threes mixture, reaction temperature 150
~170 DEG C, it is 0.5MPa, oxygen partial pressure 0.5MPa to control reaction pressure by oxygen bottle；
6) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 30~40 DEG C after residual heat recovery and condensation, and pH is 6.0~8.0, surveyed catalytic wet oxidation
Effluent index is that COD is 150mg/L；
7) waste water after gas-liquid separation enters biochemical system, residence time 10h.Bio-chemical effluent index is that CODcr is
28mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Embodiment 5
The organic silicon wastewater processing system of the present embodiment is same as Example 3.
Its processing method includes the following steps：
1) by rubber compound waste water 8000Kg after dissolved air flotation device oil removing, the low molecule in rubber compound waste water is removed, it is low
Molecule is back to the production of 107 raw rubbers, and waste water index is that CODcr is 20000mg/L, ethanol content 0.9%, pH value 7.5.
2) it by the silicones microballoon waste water 8000Kg that methanol content is 20%, CODcr 260000mg/L, pH are 9, is added
Sodium hydroxide, it is 12 to adjust pH, controls reflux ratio 1:Under the conditions of 1, rectifying to bottom temperature is 100~102 DEG C, and tower top temperature is
65~72 DEG C, recovered overhead methanol content is more than 99.5%, and tower bottoms CODcr is 8000mg/L, methanol content 0.8%；
3) it will be kneaded after glue layer and rectifying column kettle liquid mix and adjust pH to 9.0~10.0, waste water adjusts the temperature to 70~
75 DEG C, residence time 1.0h, through inorganic ions settling step, remove easy precipitating ion in waste water；
4) waste-heat is discharged to 150 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 300 DEG C；
5) waste water after heat exchange and the pre-heat treatment is with 2.0h-1Liquid air speed enter catalytic wet oxidation system, it is used negative
Supported catalyst carrier is TiO2Activated carbon, active component be Ni metal, Ru and Ni threes mixture, reaction temperature 300
DEG C, while it is 12MPa, oxygen partial pressure 5.0MPa to control reaction pressure by air compressor and oxygen bottle；
6) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 20~25 DEG C after residual heat recovery and condensation, and pH is 7.0~9.0, surveyed catalytic wet oxidation
Effluent index is that COD is 150mg/L；
7) waste water after gas-liquid separation enters biochemical system, residence time 20h.Bio-chemical effluent index is that CODcr is
28mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Embodiment 6
The organic silicon wastewater processing system of the present embodiment is same as Example 3.
1) by rubber compound waste water 8000Kg after dissolved air flotation device oil removing, the low molecule in rubber compound waste water is removed, it is low
Molecule is back to the production of 107 raw rubbers, and waste water index is that CODcr is 20000mg/L, ethanol content 0.9%, pH value 7.5.
2) it by the silicones microballoon waste water 8000Kg that methanol content is 20%, CODcr 260000mg/L, pH are 9, is added
Sodium hydroxide, it is 8 to adjust pH, controls reflux ratio 1:Under the conditions of 1, rectifying to bottom temperature is 100~102 DEG C, and tower top temperature is
65~72 DEG C, recovered overhead methanol content is more than 99.5%, and tower bottoms CODcr is 8000mg/L, methanol content 0.8%；
3) pH to 7.0~8.0 will be adjusted after glue layer and the mixing of rectifying column kettle liquid will be kneaded, waste water adjusts the temperature to 70~75
DEG C, residence time 1.0h removes easy precipitating ion in waste water through inorganic ions settling step；
4) waste-heat is discharged to 150 through heat-exchange system wet oxidation through inorganic ions settling step treated waste water
DEG C, then preheated system is warming up to 250 DEG C；
5) waste water after heat exchange and the pre-heat treatment is with 2.0h-1Liquid air speed enter catalytic wet oxidation system, it is used to urge
Agent is MgO-ZnO catalyst, and reaction temperature is 300 DEG C, while controlling reaction pressure by air compressor and oxygen bottle
For 12.0MPa, oxygen partial pressure 4.5MPa；
6) for the water outlet of catalytic wet oxidation system through separating system for water, it is existing big that unreacted air or oxygen enters factory
Gas governing system, waste water are cooled to 20~25 DEG C after residual heat recovery and condensation, and surveyed catalytic wet oxidation effluent index is COD
For 150mg/L；
7) waste water after gas-liquid separation enters biochemical system, residence time 20h.Bio-chemical effluent index is that CODcr is
28mg/L, pH=6.0~9.0 reach national grade one discharge standard.
Comparative example 1
The organic silicon wastewater processing system of this comparative example is with reference to embodiment 3, and difference lies in the waste water pretreatment system packets
Include silicones waste water pretreatment system (rectifier unit) and silicon rubber waste water pretreatment system (dissolved air flotation device), the waste water
Processing system includes that sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, biochemical treatment unit, heating unit and (changes
Heat and preheating unit), catalytic wet oxidation unit and gas-water separation unit.Change the unit connection in waste water treatment system
Order.
With reference to embodiment 3, difference lies in after step (7) is moved to step (3), that is, go the processing method of this comparative example
After easy precipitating ion in waste water, biochemical treatment is directly carried out, carries out the operation of step (4), (5) and (6) again later.
The result of this comparative example is that biochemical Systems Bacterial is all died, and biochemical system loses original function, and system water outlet refers to
It is designated as 200~500mg/L, discharge standard cannot be reached.
Based on the above embodiments with comparative example it is found that system process provided by the invention is simple, multistage oxygen is avoided
The use of change, and continuous operation greatly reduce occupation area of equipment, and have good compatibility, ingredient can be made to answer
A variety of silicones miscellaneous, type is various, biodegradability is poor, silicon rubber waste water are effectively addressed in same system.The present invention
Using the temperature and pressure that can be reduced when load type metal catalyst needed for catalytic wet oxidation, equipment investment is greatly reduced.
Comparative example does not have scheme using the present invention, thus can not obtain the effect of the present invention.
Applicant states, the foregoing is merely the specific implementation mode of the present invention, but protection scope of the present invention not office
It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention
In the technical scope of dew, the change or replacement that can be readily occurred in are all fallen within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of organic silicon wastewater processing system, which is characterized in that the system comprises sequentially connected waste water pretreatment systems
And waste water treatment system, the waste water treatment system include that sequentially connected neutralization adjusts unit, inorganic ions precipitation unit, adds
Hot cell, catalytic wet oxidation unit, gas-water separation unit and biochemical treatment unit.
2. organic silicon wastewater processing system according to claim 1, which is characterized in that the waste water pretreatment system includes
Silicones waste water pretreatment system and/or silicon rubber waste water pretreatment system；
Preferably, the silicones waste water pretreatment system includes rectifier unit；
Preferably, the rectifier unit includes rectifying column；
Preferably, the silicon rubber waste water pretreatment system includes oil-isolating device or air-floating apparatus；
Preferably, the silicones waste water is the organic silicon wastewater that alcohol content is 2%~70%；
Preferably, the silicon rubber waste water is the organic silicon wastewater that organosilicon low molecule content is 1%~40%；
Preferably, the organosilicon low molecule is the organic silicon molecule of molecular weight < 1000.
3. organic silicon wastewater processing system according to claim 1 or 2, which is characterized in that the organic silicon wastewater is silicon
Resin wastewater and/or silicon rubber waste water；
Preferably, the heating unit includes sequentially connected heat exchanger and preheater.
4. according to claim 1-3 any one of them organic silicon wastewater processing systems, which is characterized in that the catalytic wet oxygen
It includes catalytic wet oxidation device to change unit；
Preferably, the catalytic wet oxidation device is that fixed bed answers device；
Preferably, built-in load type metal catalyst in the catalytic wet oxidation device；
Preferably, the carrier of the load type metal catalyst is ceramic-absorbent charcoal, Al2O3Activated carbon, TiO2Activated carbon or
SiO2In activated carbon any one or at least two combination；
Preferably, the Al2O3Al in activated carbon2O3For γ-Al2O3；
Preferably, the metal catalytic activity substance of the load type metal catalyst be Cu, Fe, Ni, Mn, Pt, Ir, Pd, Rh or
In Ru any one or at least two combination.
5. according to claim 1-4 any one of them organic silicon wastewater processing systems, which is characterized in that the gas-water separation list
The gas vent of member is connected with air governing system；
Preferably, the biochemical treatment unit includes aerobic oxidation device；
Preferably, built-in aerobic bacteria in the aerobic oxidation device.
6. a kind of processing method of the organic silicon wastewater processing system as described in claim any one of 1-5, which is characterized in that described
Method includes the following steps：
Organic silicon wastewater is pre-processed, neutralization adjusting, inorganic is carried out successively to obtained pretreated organic silicon wastewater
After ion precipitation, heating, catalytic wet oxidation, gas-water separation and biochemical treatment, waste water up to standard is obtained.
7. processing method according to claim 6, which is characterized in that it is described pretreatment be silicones Wastewater Pretreatment and/
Or silicon rubber Wastewater Pretreatment；
Preferably, the silicones Wastewater Pretreatment includes：Rectification process is carried out to silicones waste water under alkaline condition；
Preferably, the pH of the alkaline condition is 8.0~12.0；
Preferably, the silicones waste water is after pretreatment, and dichromate oxidizability≤30000mg/L and alcohols in waste water≤
1wt%；
Preferably, the silicon rubber Wastewater Pretreatment includes：Silicon rubber waste water is handled through oil removal or air-dissolving air-float；
Preferably, the silicon rubber waste water is after pretreatment, dichromate oxidizability≤40000mg/L and organosilicon low molecule
≤ 1wt%；
Preferably, the organosilicon low molecule is the organic silicon molecule of molecular weight < 1000；
Preferably, the organic silicon wastewater is silicones waste water and/or silicon rubber waste water.
8. the processing method described according to claim 6 or 7, which is characterized in that described neutralize is adjusted the pH value adjusting of waste water
It is 6~10；
Preferably, the temperature of the inorganic ions precipitation is 60~100 DEG C；
Preferably, the residence time of the inorganic ions precipitation is 0.5~1.5h；
Preferably, the heating includes that heat exchanger heats and warming up device heating；
Preferably, waste liquid is heated to 120~150 DEG C by the heat exchanger heating；
Preferably, the heat exchanger uses the processed waste water of catalytic wet oxidation as heat source；
Preferably, waste liquid is heated to 150~300 DEG C by the preheater heating；
Preferably, the oxidant of the catalytic wet oxidation is air and/or oxygen, the preferably combination of air and oxygen；
Preferably, the catalyst of the catalytic wet oxidation is load type metal catalyst；
Preferably, the carrier of the load type metal catalyst is ceramic-absorbent charcoal, Al2O3Activated carbon, TiO2Activated carbon or
SiO2In activated carbon any one or at least two combination；
Preferably, the Al2O3Al in activated carbon2O3For γ-Al2O3；
Preferably, the metal catalytic activity substance of the load type metal catalyst be Cu, Fe, Ni, Mn, Pt, Ir, Pd, Rh or
In Ru any one or at least two combination；
Preferably, the reaction temperature of the catalytic wet oxidation is 150~300 DEG C；
Preferably, the reaction pressure of the catalytic wet oxidation is 0.5~12MPa；
Preferably, in the reaction system of the catalytic wet oxidation, oxygen partial pressure is 0.5~5.0MPa；
Preferably, the waste liquid Feed space velocities of the catalytic wet oxidation are 0.2~2h-1。
9. according to claim 6-8 any one of them processing methods, which is characterized in that the liquid phase warp that the gas-water separation generates
Subsequent biochemical treatment is carried out again after crossing condensation；
Preferably, the gas phase that the gas-water separation generates enters air governing system；
Preferably, the dichromate oxidizability for the liquid phase that the gas-water separation generates is 100~1000mg/L；
Preferably, the biochemical treatment is to carry out aerobic oxidation processing using aerobic bacteria；
Preferably, the processing time of the biochemical treatment is 10~20h；
Preferably, the inflow temperature of the biochemical treatment is 20~40 DEG C；
Preferably, the inlet flow-patterm of the biochemical treatment is 6~9；
Preferably, the dichromate oxidizability of the waste water up to standard is≤50mg/L, pH=6.0~9.0.
10. according to claim 6-9 any one of them processing methods, which is characterized in that the described method comprises the following steps：
Silicones Wastewater Pretreatment and/or silicon rubber Wastewater Pretreatment are carried out to organic silicon wastewater, it is pretreated to what is obtained
Organic silicon wastewater carries out neutralizing successively adjusting is adjusted to 6~10 by the pH value of waste water, and it is heavy that inorganic ions is carried out at 60~100 DEG C
It forms sediment, the residence time of inorganic ions precipitation is 0.5~1.5h, carries out heat exchanger heating later and waste liquid is heated to 120~150
DEG C, waste liquid is heated to 150~300 DEG C by preheater heating, then under 150~300 DEG C and 0.5~12MPa, with air and oxygen
The combination of gas is 0.2~2h to Feed space velocities with load type metal catalyst as oxidant-1Waste water carries out catalytic wet oxygen
Change, then carry out gas-water separation, to after obtained liquid phase condensate under conditions of 20~40 DEG C of temperature and 6~9 pH into acting charitably
The time of oxygen bacterium biochemical treatment, biochemical treatment is 10~20h, obtains waste water up to standard；
Wherein, the silicones Wastewater Pretreatment is that rectification process is carried out at 8.0~12.0 pH, and the silicon rubber waste water is pre-
Processing is to be handled through oil removal or air-dissolving air-float silicon rubber waste water；The carrier of the load type metal catalyst is ceramics-activity
Charcoal, γ-Al2O3Activated carbon, TiO2Activated carbon or SiO2Any one in activated carbon；The load type metal catalyst
Metal catalytic activity substance is the combination of any one or at least two in Cu, Fe, Ni, Mn, Pt, Ir, Pd, Rh or Ru；Institute
In the reaction system for stating catalytic wet oxidation, oxygen partial pressure is 0.5~5.0MPa.
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| CN110040911A (en) * | 2019-05-06 | 2019-07-23 | 孙鹏 | A kind of processing method of cupric dyeing waste water with high salt |
| CN110040911B (en) * | 2019-05-06 | 2021-07-06 | 孙鹏 | Treatment method of copper-containing high-salt printing and dyeing wastewater |
| CN114349250A (en) * | 2022-01-06 | 2022-04-15 | 万华化学集团股份有限公司 | Self-flocculation treatment method of organic silicon resin wastewater |
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