CN202658013U

CN202658013U - Biogenic manganese oxide membrane bioreactor

Info

Publication number: CN202658013U
Application number: CN2012202029956U
Authority: CN
Inventors: 李昂; 陈旭; 马放; 崔迪; 庞长泷; 张斯�; 孔祥震; 孙移鹿
Original assignee: HIT YIXING ACADEMY OF ENVIRONMENTAL PROTECTION
Current assignee: JIANGSU HIT YIXING ACADEMY OF ENVIRONMENTAL PROTECTION CO Ltd
Priority date: 2012-05-08
Filing date: 2012-05-08
Publication date: 2013-01-09
Anticipated expiration: 2022-05-08

Abstract

The utility model relates to a biogenic manganese oxide membrane bioreactor. The bioreactor comprises a reactor body, a water inlet pipe at the bottom of the reactor body, a water outlet pipe on the top of the reactor body, a reflux pipe, and an ultrafiltration membrane in the reactor body, wherein an aeration disc is arranged below the ultrafiltration membrane. The bioreactor is characterized in that a temperature control device, a pH probe and a dissolved oxygen probe are also arranged on the top of the reactor body. By the bioreactor, pharmaceutical and personal care products (PPCPs) in sewage can be oxidized by biogenic manganese oxides produced by manganese-oxidizing bacteria and removed, and oxidation intermediate products of the PPCPs can be used as a carbon source by the manganese-oxidizing bacteria and further degraded.

Description

A kind of biological manganese oxide film bio-reactor

Technical field

The utility model relates to water-treatment technology field, relates in particular to a kind of water processing reactor that contains the organic contaminant trace species of difficult degradation such as medicine and personal care articles (PPCPs).

Background technology

Nearly more than ten years more and more extensive for report and the research of medicine in the water body and personal care articles (PPCPs), and the removal of PPCPs has become the focus of domestic and international research in tap water and the sewage.PPCPs specifically refers to the general name for a large class pharmaceutical chemicals of the purposes such as medical veterinary drug, agriculture production, personal care, comprising: microbiotic, tranquillizer, anti-epileptic class medicine, the hormone of natural or synthetic, x-ray contrast agent, spices, sterilant, skin care product, sunscreen and various makeup.PPCPs content in water is very low, only is ng/L ~ μ g/L level, even if but so the PPCPs of trace also can cause serious injury to aquatic animals and plants and the mankind.Studies show that the estrogenic chemicals of trace can cause the fish sex entanglement in the water, the materials such as fluoxetine, diclofenac, gemfibrozil can be located enrichment at fish muscle, liver, brain etc., cause the biological accumulation effect.

At present, conventional tap water and sewage treatment process are difficult to efficiently remove the PPCPs in the water, traditional activated sludge process and membrane bioreactor are mainly removed PPCPs in the water by absorption and biological degradation when water treatment, but the removal ability is very limited, and the PPCPs that is adsorbed on the active sludge is difficult to further explanation, can enter along with the subsequent disposal of mud in the surrounding medium such as soil, cause secondary pollution.The PPCPs removal method that other is widely studied mainly comprises chlorination, ozone oxidation and ultraviolet/hydrogen peroxide (UV/H ₂O ₂), the senior oxidation technology (AOPs) such as Fenton (Fenton) oxidation.Although these methods are mineralising PPCPs class material effectively, they all have an outstanding shortcoming, i.e. high energy consumption, high processing costs, this also so that these method for oxidation can not use in water treatment system on a large scale.

Summary of the invention

In order to overcome above-mentioned technical deficiency, the utility model provides a kind of biological manganese oxide film bio-reactor of can economical and efficient removing PPCPs and other organic micro-pollutants in the water.

A kind of biological manganese oxide film bio-reactor, comprise reactor, the water inlet pipe of reactor bottom, the rising pipe at top, return line, the ultra-filtration membrane of inside reactor, the below of ultra-filtration membrane is equipped with aeration plate, it is characterized in that ultra-filtration membrane is that manganese oxidation bacterium and Mn oxide are trapped in the composite membrane on hollow-fibre membrane or the board-like tunica fibrosa.Disposing of sewage enters from reactor bottom, and the bottom-up reactor of flowing through is from the discharge of reactor head.

Reactor head is provided with temperature control unit, pH probe and dissolved oxygen probe in addition, remains dissolved oxygen in the dissolved oxygen probe monitoring reaction device; Reactor bottom is provided with shore pipe in addition.

Above-mentioned reactor can utilize PPCPs in the biological manganese oxide compound oxidation removal sewage that manganese oxidation bacterium produces, its intermediate oxidation product can be by manganese oxidation bacterium as utilization of carbon source further to be degraded.

Contain the method for PPCPs sewage with this reactor for treatment, may further comprise the steps:

(1) preparation biological manganese oxide compound bacteria suspension: adopt bacterium pure culture mode to cultivate manganese oxidation bacterium, utilize manganese oxidation bacterium oxidation Mn ²⁺Produce the biological manganese oxide compound, wherein Mn in the biological manganese oxide compound ⁴⁺Reach 50-60mg/L.Manganese oxidation bacterium can be selected known to Mn ²⁺Have the microorganisms such as bacterium oxidation effectiveness, that can produce Mn oxide, fungi, the content of biological manganese oxide compound is the MnCl that adds by in the quantitative control nutrient solution ₂Amount realizes;

(2) the biological manganese oxide composite membrane forms: pass into continuously the biological manganese oxide compound bacteria suspension for preparing in the step (1) in the reactor, saturated aeration, reaction 14h combines closely on the hollow-fibre membrane or board-like film in reactor manganese oxidation bacterium and Mn oxide.The material of hollow-fibre membrane or board-like film can be commercially available polysulfones, polyethersulfone, polymeric amide, polyacrylonitrile, polyvinylidene difluoride (PVDF), cellulose ester, polyether-ether-ketone, pi, polyetheramides etc., adopts the circumferential water feed central water outlet; Aeration control is at 1.3-1.5L/h;

(3) operation of reactor: reactor adopts succession running, upward flow, and liquid pH is controlled at 6.5-6.8(pH and uses NaH in the reactor ₂PO ₄Or Na ₂HPO ₄Buffered soln is regulated), the residue Dissolved Oxygen concentration Control is at 2-3mg/L, and temperature is controlled to be 26-28 ℃, and hydraulic detention time is controlled at 8-12 hour.

Contain PPCPs sewage and pass into continuously in the reactor, the upward flow water outlet, in reaction process, the Mn in the biological manganese oxide compound ⁴⁺Be reduced to Mn ²⁺, manganese oxidation bacterium can be with Mn ²⁺Be oxidized to Mn ⁴⁺, guaranteed carrying out smoothly of PPCPs oxidizing reaction.The PPCPs material that originally can not be utilized by manganese oxidation bacterium is after Mn oxide oxidative degradation, and generation can be by the intermediate product of microorganism as utilization of carbon source, thereby further degraded by microorganism.

Compared with prior art, the utlity model has following advantage and effect:

The utility model biological manganese oxide compound oxidation style has broad spectrum to the PPCPs removal of pollutants, the intermediate product of PPCPs oxidative degradation often can be as the used carbon source of manganese oxidizing bacteria growth, thereby further degraded, can be prevented effectively that the PPCPs intermediates from entering the pollution that water body causes; The Mn that Mn oxide oxidation PPCPs produces ²⁺Accumulation can hinder further carrying out of oxidizing reaction, and the existence of manganese oxidation bacterium can be with Mn ²⁺Be oxidized to Mn ⁴⁺, constantly the Mn oxide concentration in the postreaction guarantees carrying out smoothly of reaction, this is in traditional MnO ₂Oxidation PPCPs has more high efficiency and need not continue to add MnO ₂, more economical; In the PPCPs of the high energy consumptions such as ozone oxidation and high-level oxidation technology removal method, the utility model utilizes microorganism so that Mn ⁴⁺In-situ regeneration utilizes in the sewage organism as manganese oxidizing bacteria growth required carbon source and the energy, and is more economical and practical.

Description of drawings

Fig. 1 is the structural representation of the utility model reactor.

Embodiment

Below in conjunction with the drawings and specific embodiments the technical solution of the utility model is described further:

Embodiment 1

A kind of biological manganese oxide film bio-reactor, comprise reactor, the water inlet pipe 4 of reactor bottom, the rising pipe 6 at top, return line 7, the ultra-filtration membrane 11 of inside reactor, the below of ultra-filtration membrane 11 is equipped with aeration plate 8, ultra-filtration membrane 11 is that manganese oxidation bacterium and Mn oxide are trapped in the composite membrane on hollow-fibre membrane or the board-like tunica fibrosa, and reactor head is provided with temperature control unit 1, pH probe 2 and dissolved oxygen probe 3 in addition, and reactor bottom is provided with shore pipe 9 in addition.

(1) preparation biological manganese oxide compound bacteria suspension

With manganese oxidation inoculation in be equipped with manganese oxidation bacteria culture fluid in the triangular flask that high pressure steam sterilization is processed, in constant-temperature table (26 ℃, cultivate 18h in 120rpm), manganese oxidation this moment bacterium reaches mid-term stationary phase of growth.Manganese oxidation bacterium is spread cultivation to 10L bacterial classification stoste, be inoculated in 100L with 10% inoculum size and add 126g MnCl ₂Manganese oxidation bacteria culture fluid fermentor tank in, at pH 6.8-7.0,26 ℃ of temperature, rotating speed 140rpm cultivates 48h under the dissolved oxygen 1:1 condition, this moment Mn ²⁺All be oxidized to Mn ⁴⁺Take out nutrient solution centrifugal 10 min under 7500 r/min conditions, abandoning supernatant, with throw out 0.01M, the phosphate buffer solution of pH7.0 cleans twice, makes biological manganese oxide compound bacteria suspension.

The composition of manganese oxidation bacteria culture fluid is to add 0.5g yeast extract paste, 0.5g casamino acids, 1g glucose, 2.38g HEPES buffer reagent, 0.222g CaCl in every 1L distilled water ₂, 0.8118g MgSO ₄7H ₂O, 0.01g FeCl ₃6H ₂O, 1ml trace element solution.

The trace element solution compound method is to add 10mg CuSO in every 1L distilled water ₄5H ₂O, 44mg ZnSO ₄7H ₂O, 20mg CoCl ₂6 H ₂O, 13mg Na ₂MoO ₄2H ₂O.

(2) manganese oxidation bacterium and Mn oxide composite membrane form

The 100L biological manganese oxide compound bacteria suspension for preparing in (1) is passed in the reactor, manganese oxidation bacterium and biological manganese oxide compound are held back by tubular fibre, continue to pass into manganese oxidation bacteria culture fluid in the reactor in the cultured continuously mode, continue aeration with the 1.3-1.5L/h aeration rate, make that dissolved oxygen is state of saturation in the reactor, behind the reaction 14h, in the reactor on thalline apposition growth and the hollow-fibre membrane, and thalli growth reaches logarithmic phase latter stage, early stage stationary phase, has higher reactive behavior, and because the tiny aperture of Polyethersulfone Hollow Fiber Plasma, biological manganese oxide compound and tubular fibre are closely compound.

(3) reactor operation

1. the parameter of disposing of sewage

PPCPs sewage I adopts secondary effluent from sewage treatment plant, main water-quality guideline: COD 50-60mg/L, PO ₄ ^3--P 0.6-0.1mg/L, NH ₄ ⁺-N 3.0-3.8 mg/L, NO ₃ ^--N 7.8-9.5mg/L; PPCPs concentration: Carbamzepine 15-23 μ g/L, sulfamethoxazole 630-680 ng/L, 17 α-Ethinylestradiol 10-26ng/L, 17 beta estradiol 31-48ng/L, oestrone 65-90 ng/L, trihydroxy-oestrin 130-169 ng/L.

What PPCPs sewage II adopted the laboratory preparation contains the phosphate buffer solution that steroid oestrogenic hormon 17 α-Ethinylestradiol, 17 beta estradiols, oestrone, trihydroxy-oestrin be 1mg/L (every 1mg estrogen substance with the 25ml dissolve with methanol then add in the buffered soln), NaCl 0.6g/L regulates pH 6.7.

2. sewage disposal stage

Reactor adopts continuously-running duty.PPCPs sewage is entered in the reactor through peristaltic pump 10 by water inlet pipe 4, bottom-up flowing.Current enter in the film through the outside of hollow-fibre membrane 11, are discharged from water outlet by tunica fibrosa inside again.Wherein a part of sewage in the tunica fibrosa outside is back in the water inlet pipe 4 via return line 7, and reflux ratio is controlled at about 30% by manually-operated gate A3 and under meter Q3.The air that is pumped into by air compressor machine 5 is through aeration plate 8 continuous aeration in the reactor, and aeration rate is controlled at 1.3-1.5L/h by pneumavalve J1.Biological manganese oxide compound compound in the step (2) will be through the PPCPs substance oxidation degraded of hollow-fibre membrane, and its intermediate oxidation product part continues by biological manganese oxide compound oxidation permineralization, and another part is degradable as utilization of carbon source by manganese oxidation bacterium.In reaction process, the Mn in the biological manganese oxide compound ⁴⁺Be reduced to Mn ²⁺, its reaction equation is as follows:

MnO _{2(
Biological)}+ 4H ⁺+ 2e ^-→ Mn ²⁺+ 2H ₂O (1)

PPCPs(or its intermediate oxidation product) as electron donor, with transfer transport to electron acceptor(EA)-biological manganese oxide compound, Mn ²⁺Accumulation can hinder the further generation of reaction, and " biofilm " can be with Mn the manganese oxidation bacterium on tubular fibre surface ²⁺Be oxidized to Mn ⁴⁺, guaranteed carrying out smoothly of PPCPs oxidizing reaction.The PPCPs material that originally can not be utilized by manganese oxidation bacterium is after Mn oxide oxidative degradation, and generation can be by the intermediate product of microorganism as utilization of carbon source, thereby further degraded by microorganism.

3. reactor operational conditions control

Reactor head is equipped with temperature control unit 1, pH probe 2 and dissolved oxygen probe 3.Temperature is controlled at 26-28 ℃, to guarantee the required temperature environment of manganese oxidizing bacteria growth; PH is controlled to be 6.5-6.8, has at first guaranteed the normal growth of manganese oxidation bacterium, and by formula (1) as seen, H ⁺Have carrying out that is beneficial to reaction, so the slant acidity environment can improve biological manganese oxide compound oxidation PPCPs usefulness; Dissolved oxygen probe 3 is positioned at the water side, and measured residue Dissolved Oxygen concentration Control is at 2-3 mg/L.

By regulating the Inlet and outlet water flow, hydraulic detention time should be controlled at 8-12h, to reach comparatively desirable treatment effect.

4. reactor operating performance

After testing, the utility model has obvious removal effect to PPCPs material in the sewage.For actual sewage treatment plant secondary effluent (PPCPs sewage I), in the materials such as the Carbamzepine of monitoring, sulfamethoxazole and oestrogenic hormon, the sulfamethoxazole that clearance is minimum and 17 α-Ethinylestradiol clearance is respectively 71% and 82%, and the clearance of all the other materials is all more than 85%; For the PPCPs II sewage of higher concentration (1mg/L), the utility model also can reach comparatively desirable removal effect, and except the clearance of 17 α-Ethinylestradiol is 68%, the clearance of all the other materials is all more than 80%.As seen the utility model not only has preferably removal effect to high density PPCPs sewage, be more applicable in the middle of the city sewage deep treatment, the utility model is when removing PPCPs, the oxygenizement of Mn oxide can improve the biodegradability of sewage equally, thereby makes in the sewage not removed organic matter be utilized and obtain degraded by microorganisms such as manganese oxidation bacterium.

Above-described embodiment only is explanation technical conceive characteristics of the present utility model, and its purpose is to allow the personage who is familiar with technique can understand the utility model and according to this enforcement, can not limit protection domain of the present utility model with this.All equivalences of doing according to the utility model spirit change or modify, and all should be encompassed within the protection domain of the present utility model.

Claims

1. biological manganese oxide film bio-reactor, comprise reactor, the water inlet pipe of reactor bottom, the rising pipe at top, return line, the ultra-filtration membrane of inside reactor, the below of ultra-filtration membrane is equipped with aeration plate, it is characterized in that reactor head is provided with temperature control unit, pH probe and dissolved oxygen probe in addition.

2. a kind of biological manganese oxide film bio-reactor according to claim 1 is characterized in that reactor bottom is provided with shore pipe in addition.