CN210176671U - High-salt high-concentration degradation-resistant organic wastewater treatment equipment - Google Patents
High-salt high-concentration degradation-resistant organic wastewater treatment equipment Download PDFInfo
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
A high-salt high-concentration degradation-resistant organic wastewater treatment device comprises the following structures: the device comprises a pretreatment device containing a composite catalytic oxidation device, an electrodialysis device connected behind the pretreatment device, a salt collecting and making device with a butt joint of concentrated water ports of the electrodialysis device, one or more deep purification devices of an anaerobic reactor, an electrocatalysis flocculator or a biological denitrifier with a butt joint of fresh water ports of the electrodialysis device, and a reverse osmosis device. The equipment is used for treating high-salt high-concentration degradation-resistant organic wastewater, so that the defects that the high-salt high-organic degradation-resistant complex wastewater is unstable in operation in a biochemical process, and microorganisms die in a large amount and cannot stably operate for a long time are overcome; the method solves the problem that toxic and harmful substances in the high-salt high-organic-matter degradation-resistant complex wastewater influence and damage the electrodialysis membrane, prolongs the service life of the membrane and reduces the operation cost. The deep purification device is combined for treatment, so that the generation amount of chemical sludge is reduced, and the whole system is more economical.
Description
Technical Field
The utility model relates to a wastewater treatment device, in particular to a high-salt high-concentration degradation-resistant organic wastewater treatment device.
Background
High salinity wastewater refers to wastewater with salinity higher than 1%. The high-salinity wastewater is toxic and difficult to degrade, and a large amount of high-salinity wastewater is generated in the fields of printing and dyeing, papermaking, chemical industry, oil refining, seawater utilization, oil field wastewater and the like. The high-salinity wastewater is generally diluted and discharged outside, which causes water resource waste, and the total pollution amount is unchanged, which also causes adverse effects on the environment, so that research on an effective treatment method of the high-salinity wastewater is urgent.
The organic matter of the high-salt organic wastewater has great difference in the types and chemical properties of the organic matter according to different production processes, but most of the salt substances are Cl-、SO4 2-、Na+、Ca2+And the like. Although these ions are essential nutrients for the growth of microorganisms, if the concentration of these ions is too high, they may have inhibitory and toxic effects on microorganisms. The high-salinity wastewater has high salt concentration and high osmotic pressure, and the microbial cell dehydration causes cell protoplast separation; the salting-out action reduces the dehydrogenase activity; the chloride ion has toxic action on cells; the salt concentration is high, the wastewater density is increased, and the activated sludge is easy to float and run off, thereby seriously influencing the purification effect of biological treatment. Common biochemical processes are difficult to handle.
In recent years, the attention on high-salinity wastewater is higher and higher, continuous innovation is also carried out on the wastewater treatment system and the process technology, Chinese utility model patent specification CN109354241A discloses an industrial high-salinity wastewater zero-discharge treatment system and method rich in refractory organic matters, the method is that the high-salinity wastewater is subjected to filtration pretreatment mechanism to remove impurities affecting electrodialysis concentration and subsequent crystallized salt purity, such as hardness, colloid, suspended matters, dissolved silicon and the like, the concentrated solution is subjected to electrodialysis treatment after filtration, the concentrated solution is crystallized to prepare salt, and the desalted solution is subjected to partial organic matters through advanced oxidation degradation and further desalted by a reverse osmosis concentration mechanism. The treatment technology combines electrodialysis and advanced oxidation technology, and is not suitable for high-salt high-concentration refractory wastewater, firstly, substances such as hardness, colloid, suspended matters, dissolved silicon and the like are only pretreated at the front section of electrodialysis, toxic and harmful organic matters in the high-salt high-concentration complex refractory wastewater still remain in water, the service life of an electrodialysis membrane is seriously influenced, the running cost is increased, the rear end is connected with the advanced oxidation technology, the dosage of a medicament for advanced oxidation is large, and the oxidizability of high chloride ions is inhibited.
The utility model discloses a zero release treatment process of high salt waste water is disclosed in chinese utility model patent specification CN108409050A, this kind of method is earlier with high salt waste water entering AO biochemical system carry out anaerobic treatment and aerobic treatment, it has the pollutant to get rid of most, reduce the COD content of high salt waste water, then get into 1# high pressure reverse osmosis membrane system through MBR membrane system, the liquid that dams does not directly discharge or carry out the crystallization, but reuse high pressure nanofiltration membrane system and carry out the branch liquid, carry out preliminary minimizing to waste water, and improve the purification purity who divides the salt. The method has the disadvantages that biochemical pretreatment is adopted firstly, if the salt content is higher than 2 percent and even higher, the growth of microorganisms is seriously inhibited and even loses water to die, the biochemical stability is poor, the biochemical section is difficult to carry out, a large amount of dead mud is attached to effluent, suspended matters are increased, the high-pressure reverse osmosis membrane is easy to block, the chemical cleaning frequency is increased, the service life of the membrane is reduced, and the operation cost is increased.
For electroosmosis fresh water production, when inorganic salt is concentrated to 20% of mass concentration by electrodialysis, organic matters in inlet water are intercepted on the fresh water side, the problem of continuous enrichment of the organic matters also needs to be considered when the fresh water side is subjected to advanced treatment and recycling, the higher the organic matter concentration is, the more easily the reverse osmosis membrane is polluted, most advanced oxidation technologies are interfered by the concentration of chloride ions in the electroosmosis fresh water to influence the efficiency of degrading the organic matters, and the organic matters need to be degraded by using a multi-stage advanced oxidation technology. Especially, in the prior art, a high-pressure reverse osmosis membrane concentration system needs frequent chemical cleaning, the problem of organic matter blockage is relieved, and the service life of the membrane is very short. The investment cost and the operation cost of the whole process are high, and the economic high-salinity wastewater treatment standard-reaching discharge is difficult to realize
Among all concentration techniques, electrodialysis is the most mature and economical technique for concentrating high-salt-content wastewater at present, and has great advantages in the field because the electrodialysis can concentrate soluble inorganic salt to a mass concentration of more than 20% and approach to saturation solubility at one time. In order to treat high-salt and high-concentration wastewater by electrodialysis, the problems of pretreatment and subsequent advanced treatment must be solved.
SUMMERY OF THE UTILITY MODEL
The utility model aims to solve the above problems and provide a high-salt high-concentration degradation-resistant organic wastewater treatment device, the treatment device comprises the following structures: the device comprises a pretreatment device containing a composite catalytic oxidation device, an electrodialysis device connected behind the pretreatment device, a concentrated water port of the electrodialysis device is butted with a collecting salt making device, and a fresh water port of the electrodialysis device is butted with one or more deep purification devices of an anaerobic reactor, an electrocatalysis flocculator and a biological denitrifier and then is butted with a reverse osmosis device.
The composite catalytic oxidation device comprises a cavity capable of containing wastewater, a carrier filled with porous composite materials is filled in the cavity, the carrier is pre-filled with noble metals, rare earth metals or transition metals and oxides thereof and redox reaction catalysts, the device is also provided with a pipeline or an opening for adding medicaments, and the bottom of the device is provided with an aeration device. For example, ceramic balls can be used as the support. Using MnO2As metal oxide on a support, and ferrous iron is added as a catalyst.
The aeration device at the bottom of the composite catalytic oxidation device enables the surface of the catalyst to be stirred by large kinetic energy of gas and liquid, and three-phase substances are violently impacted, so that the adsorption and desorption reaction efficiency is greatly increased, and solid impurities are prevented from being accumulated on the surface of the catalyst, so that the catalyst is poisoned and the catalytic efficiency is reduced.
The catalyst is selected from any one of ferric salt, ferrous salt and copper salt. Preferably said iron saltIs FeCl3、Fe(OAc)3Or Fe2(SO4)3The ferrous salt is FeCl2、Fe(OAc)2、 FeSO4。
Adopt compound catalytic oxidation to do the preliminary treatment, be different from other preliminary treatments and only get rid of suspension organic matter and colloidal pollutant through chemical flocculation or mechanical filtration's mode, simple chemical flocculation or mechanical filtration's mode does not have any effect of getting rid of to ketone and carbocycle class material and oil and fat, and there is the poisoning effect to the electrodialysis membrane through experiment ketone and carbocycle class material and oil and fat, and the preliminary treatment of this system is got rid of and utility model to this type of toxic material has. The filling material is used to pre-load the composite catalyst, the dosage of the medicament is extremely low, the catalyst is on the carrier and can not float along with the sludge, the loss is reduced, the dosage of the medicament is large when the common chemical oxidation is used for high-concentration organic wastewater, a large amount of ferric salt precipitation is generated, the sludge amount is large, and the operation cost is high, so the composite catalytic oxidation process has remarkable advantages; the pretreatment of the composite catalytic oxidation aims to reduce a large amount of toxic and harmful substances, quantitative oil and lipid substances in the high-salt high-concentration organic wastewater, reduce the damage to an electrodialysis membrane, and simultaneously degrade macromolecules by the catalytic oxidation process to make the macromolecules become micromolecules, so that the organic matters on the fresh water side after electrodialysis are easier to carry out anaerobic biochemical treatment.
Furthermore, the pretreatment equipment is sequentially connected with a precipitation filtration reactor, a softening reaction device, a manganese sand multi-medium filter, an intermediate water tank and a precision filter after the composite catalytic oxidation device.
The sedimentation and filtration reactor is characterized in that a filter screen is arranged in a sedimentation tank. The sedimentation and filtration reactor is different from any independent sedimentation and filtration, not only is a combined process of sedimentation and filtration, but also is characterized in that a filter screen is arranged in a sedimentation tank, sludge is separated by the filter screen in the reactor, liquid flows out through the filter screen, the sludge is gradually gathered along with the increase of the sludge amount, a sludge filter layer with good compactness is formed in the filter screen, and the purification purpose is achieved through the adsorption and filtration of the filter layer.
Softening treatment is added, so that the hardness of the wastewater and other heavy metal pollutants can be better removed, and the membrane surface can be prevented from crusting due to the generation of precipitate substances caused by sulfate ions, calcium, magnesium and other metals in the wastewater in the electrodialysis process in the high-salinity wastewater. The manganese sand filter is used for removing the residual iron ions in the first step in the water and the iron and manganese ions in the water. The middle water tank is used for homogenizing and adjusting the flow.
After softening treatment, the wastewater enters an acid-base neutralization pool through a precision filter for neutralization, and the wastewater is ensured to be neutral or slightly acidic before being subjected to electrodialysis, wherein the precision filter in the step is made of pp material and is a 0.45-micron filter element filter.
The electrodialysis equipment is connected behind the pretreatment equipment, and the concentrated water port of the electrodialysis equipment is in butt joint with the collection salt making equipment, so that the salt can be made through crystallization and separated. The fresh water port of the electrodialysis device is connected with one or more deep purification devices of the anaerobic reactor, the electrocatalysis flocculator and the biological denitrogenation device, and then is connected with the reverse osmosis device.
The anaerobic reactor is mainly used for removing a large amount of organic pollutants, reducing COD and removing phosphorus. The electrocatalysis flocculator breaks long chains and ring chains in sewage by utilizing high voltage, and crushes macromolecules into micromolecules, so that the biodegradability is improved, the load of a biochemical system is reduced, and the stability of biochemical treatment is improved. The biological denitrifier performs denitrification and further removes residual degradable organic matters. Preferably, the anaerobic reactor, the electrocatalytic flocculator and the biological denitrifier are connected in series in sequence.
Furthermore, a filter and a sedimentation tank are sequentially arranged before the reverse osmosis membrane system and after the deep purification equipment. Preferably, a sand flow filter may be used. The quicksand filter aims to remove fine suspended matters in the denitrified effluent and reduce the problem of blockage of a high-pressure reverse osmosis membrane. Thus, the impurities can not cause the damage of the reverse osmosis membrane after the water outlet is set to be precipitated.
The pre-installed composite catalyst in the composite catalytic oxidation device is formed by compounding various metals and transition metals, and the reaction is as follows:
≡Mn++H2O2<＝>M(n+1)++OH-+HO·
≡M(n+1)++HOO·→≡Mn++O2+H-
≡Mn++≡N(m+1)+→≡M(n+1)++≡Nm+
by using the device, the oxidation-reduction cycle capacity of the catalyst is enhanced rapidly, the degradation capacity is improved, the molecular surface performance of the synthesized metal catalyst is better, and the adsorption and mechanical strength performance of the catalyst are further improved.
In the composite catalytic oxidation process, a porous composite material is used as a carrier, noble metal, rare earth metal and transition metal are used as fillers, a catalyst is selected from any one of ferric salt, ferrous salt and copper salt, wastewater is adjusted to be acidic, and H is added2O2And initiating redox reaction, and completing aeration.
Has the advantages that:
1. the utility model discloses an it is directly biochemical not to adopt, because high salt waste water is higher than more than 1% at salt content, can cause the inside and outside osmotic pressure of microbial cell different to the dehydration is dead, and salt-tolerant fungus is difficult for cultivateing, and the salt-tolerant fungus of cultivateing out does not have the hereditary feature, has to rise too big still can cause the good salt-tolerant fungus of a large amount of cultivations to die when salt content, is unfavorable for the long-term steady operation of biochemical technology. The salt content is controlled to be relatively stable and a lower value by using electrodialysis for desalination, so that the biochemical section is more stable in order to avoid the death of halotolerant bacteria caused by the large change of the salt content in the environment, and the microbial growth and reproduction are more facilitated by maintaining the environment with relatively low salt, and the defects that the operation of high-salt high-organic matter degradation-resistant complex wastewater in the biochemical process is unstable, and the long-term stable operation cannot be realized due to the mass death of microorganisms are solved;
2. the front section of electrodialysis adopts a composite catalytic oxidation process, so that not only are substances such as colloids, suspended matters and dissolved silicon removed, but also a part of organic matters which are difficult to oxidize under the influence of high chlorine are removed;
3. after electrodialysis desalination, fresh water enters an anaerobic system, after anaerobic digestion, effluent passes through electrocatalysis flocculation and enters a denitrification system, the process links an anaerobic process and aerobic denitrification through electrocatalysis flocculation, partial dead mud brought in the anaerobic effluent and different types of sludge and microorganisms are guaranteed not to influence a subsequent denitrification system, meanwhile, long chains and ring chains in sewage are broken by utilizing high voltage of the electrocatalysis flocculation, macromolecules are broken into micromolecules, thus biodegradability is improved, load of the subsequent biochemical system is reduced, and stability of biochemical treatment is improved. The operation of a denitrification system is more facilitated, the operation is superior to that of an advanced oxidation system, a large amount of organic components are utilized, energy regeneration is carried out through anaerobism, the generation amount of chemical sludge is reduced, and the whole system is more economical.
Drawings
FIG. 1 schematic diagram of the apparatus
FIG. 2 apparatus flow chart
FIG. 3 shows the results of different wastewater treatment
Wherein 1 is a composite catalytic oxidation pretreatment device, 2 is an electrodialysis device, 3 is a salt collecting and making device, 4 is an anaerobic reactor, 5 is an electrocatalytic flocculator, 6 is a biological denitrifier, and 7 is a reverse osmosis device
The specific implementation mode is as follows:
example 1
A high-salt high-concentration degradation-resistant organic wastewater treatment device comprises a pretreatment device of a composite catalytic oxidation device 1, wherein an outlet of the pretreatment device is connected with a water inlet of an electrodialysis device 2, a concentrated water outlet of the electrodialysis device 2 is connected with an inlet of a device for collecting salt 3, a fresh water outlet of the electrodialysis device 2 is connected with a water inlet of an anaerobic reactor 4, a water outlet of the anaerobic reactor 4 is connected with a water inlet of an electrocatalysis flocculator 5, a water outlet of the electrocatalysis flocculator 5 is connected with a water inlet of a biological denitrifier 6, a water outlet of the biological denitrifier 6 is connected with a reverse osmosis device 7 in a butt joint mode, and a concentrated water outlet.
Wherein, the pretreatment equipment can adopt equipment such as composite catalytic oxidation 1, softening equipment, a multi-medium filter, a precision filter and the like to primarily purify and degrade substances which have influence on the membrane, such as toxic and harmful substances, colloids, suspensions, grease and the like in the wastewater;
the electrodialysis device 2 adopts a high-pollution-resistance alloy membrane, has certain tolerance degree on other toxic and harmful substances such as grease, COD and the like, and carries out salt separation on high-salt high-concentration nondegradable organic wastewater.
Wherein, the anaerobic reactor 4 can be selected from UASB, EGSB, IC and other devices which can achieve the purpose of degrading high-concentration COD;
wherein, the electrode plate of the electrocatalysis flocculator 5 can be selected from iron, aluminum, stainless steel, titanium and mixed electrodes thereof;
wherein, the biological denitrifier 6 can be selected from other reactors with the functions of denitrogenation and COD removal, such as A/O, anaerobic ammonia oxidation and the like.
Example 2
The example adopts that the complicated difficult degradation organic waste water of high salt high concentration adopts a certain company of Shandong to collect the mud waste water that oil field drilling platform produced, and the mud waste water contains a large amount of solid matter, and the water sample outward appearance is dark green after the flocculation and precipitation is handled, contains TDS 85000mg L, COD9000 ~ 12000mg/L, NH 3-N58.5 mg/L, total nitrogen 105mg/L, contains a large amount of drilling fluid additive and surfactant active, and total hard all is about 2500mg/L, uses the utility model discloses an equipment handles this waste water.
(1) Adding the slurry wastewater into a reaction tank containing a carrier catalyst MnO2, adjusting the pH to 3-4 by using sulfuric acid, and then adding the slurry wastewater: ferrous sulfate: hydrogen peroxide is 1 t: 3 kg: 3L of the mixture is uniformly stirred, after internal aeration is carried out for 10 hours, sodium hydroxide is used for adjusting the pH to 7-8, and the pH is adjusted to be 3600 COD3600mg/L through a precipitation filter;
(2) after the wastewater flows into a softening device from an outlet of a precipitation filter, the total hardness is below 100mg/L, lime-soda ash is used, the adding amount is controlled according to the pH value, lime is added until the pH value is 10, soda ash is added, the hardness and other heavy metal substances of the muddy water are removed, clear liquid is pumped into a manganese sand filter through a corrosion-resistant pump to remove the iron ions remained in the step (1) and the manganese ions in the wastewater, filtrate flows into an intermediate water tank to adjust the water quality and water quantity, and then is pumped into a precision filter through an acid-alkali resistant pump to be filtered;
(3) neutralizing the filtrate in an acid-base neutralization tank by using hydrochloric acid, adjusting the pH to 6-7, desalting by using a high anti-pollution electrodialysis membrane, allowing concentrated water to flow into a concentrated water tank for crystallization and salt preparation, allowing fresh water to flow into a fresh water tank, and pumping into an anaerobic reactor by using a pump, wherein in the embodiment, a UASB (anaerobic sludge bed) anaerobic reactor is used for carrying out anaerobic treatment, the retention time is 10 days, and the COD (chemical oxygen demand) of anaerobic effluent is 700-800 mg/L;
(4) anaerobic effluent flows into an electrocatalysis flocculation device, under the action of a high-voltage electric field, a suspension body is removed, colloid and macromolecules are smashed into micromolecules, so that the biodegradability is improved, denitrification is carried out by entering a denitrification process, the effluent passes through a sedimentation tank and is pumped into a quicksand filter by a pump, the effluent quality is 300-400 mg/L of COD (chemical oxygen demand), NH3-N15 mg/L-20 mg/L of water is filtered by the quicksand filter, further desalination and removal of residual organic matters are carried out through a high-voltage reverse osmosis membrane, the effluent can reach the first-level standard of comprehensive sewage discharge, and the concentrated solution of high-voltage reverse osmosis returns to the front section of a precision filter and is.
Example 3
Utilize the utility model discloses a device, handle the waste water of difference, the testing result of each section waste water that gains is shown in figure 3.
Claims (7)
1. A high-salt high-concentration degradation-resistant organic wastewater treatment device is characterized by comprising the following structures: the device comprises a pretreatment device containing a composite catalytic oxidation device, an electrodialysis device connected behind the pretreatment device, a concentrated water port of the electrodialysis device is butted with a salt making device, and a fresh water port of the electrodialysis device is butted with one or more deep purification devices of an anaerobic reactor, an electrocatalysis flocculator or a biological denitrifier and then butted with a reverse osmosis device.
2. The apparatus as claimed in claim 1, wherein the composite catalytic oxidation apparatus comprises a chamber for wastewater to pass through, the chamber is filled with a porous composite material carrier, and the carrier is pre-filled with a redox reaction catalyst.
3. The equipment for treating high-salt high-concentration degradation-resistant organic wastewater according to claim 1 or 2, wherein the composite catalytic oxidation device is further provided with a pipeline or an opening for adding a medicament.
4. The apparatus for treating high-salt high-concentration degradation-resistant organic wastewater according to claim 1 or 2, wherein an aeration device is arranged at the bottom of the composite catalytic oxidation device.
5. The apparatus for treating high-salt high-concentration organic wastewater difficult to degrade according to claim 1, wherein the pretreatment apparatus is further sequentially connected with a precipitation filtration reactor, a softening reaction device, a manganese sand multi-medium filter, an intermediate water tank and a precision filter after the composite catalytic oxidation device.
6. The apparatus for treating high-salinity high-concentration refractory organic wastewater according to claim 5, characterized in that the precipitation filtration reactor is provided with a filter screen in the precipitation tank.
7. The apparatus for treating high-salinity high-concentration refractory organic wastewater according to claim 1, characterized in that a sedimentation tank and a filter are sequentially arranged before the reverse osmosis membrane system and after the deep purification apparatus.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912131A (en) * | 2019-04-12 | 2019-06-21 | 宇恒(南京)环保装备科技有限公司 | A kind of high concentration hard-degraded organic waste water processing equipment with high salt and technique |
| CN111762926A (en) * | 2020-06-09 | 2020-10-13 | 轻工业环境保护研究所 | A method for electrocatalysis-low pressure reverse osmosis treatment of industrial wastewater |
| CN112624519A (en) * | 2020-12-29 | 2021-04-09 | 重庆理工大学 | Treatment method of preserved szechuan pickle wastewater |
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2019
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912131A (en) * | 2019-04-12 | 2019-06-21 | 宇恒(南京)环保装备科技有限公司 | A kind of high concentration hard-degraded organic waste water processing equipment with high salt and technique |
| CN111762926A (en) * | 2020-06-09 | 2020-10-13 | 轻工业环境保护研究所 | A method for electrocatalysis-low pressure reverse osmosis treatment of industrial wastewater |
| CN112624519A (en) * | 2020-12-29 | 2021-04-09 | 重庆理工大学 | Treatment method of preserved szechuan pickle wastewater |
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