CN101671624B - Reaction unit for sludge acclimation and polyhydroxyalkanoates synthesis by sludge and synthetic method thereof - Google Patents
Reaction unit for sludge acclimation and polyhydroxyalkanoates synthesis by sludge and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses a reaction unit for sludge acclimation and polyhydroxyalkanoates synthesis by sludge and a synthetic method thereof, and provides a reaction unit which is applicable for large-scale industrial production and has simple structure, convenient operation and low cost for sludge acclimation and polyhydroxyalkanoates synthesis by sludge as well as a method which adopts the reaction unit and has higher sludge synthetic yield for sludge acclimation and polyhydroxyalkanoates synthesis by sludge. The reaction unit is provided with a sludge domestication device and a synthesis reactor; the sludge domestication device is provided with a domestication retort and an aerator; and the synthesis reactor is provided with a constant temperature water bath, a synthesis retort, two microcomputer time controllers, an aerator and a stirrer. Activated sludge is taken and put into the domestication retort, continuous domestication is conducted by taking water feed, aerobic aeration, spoil disposal, sedimentation and water outlet as a domestication period to obtain stably-domesticated sludge, then the sludge is put into the synthesis retort while taking acetic acid as the carbon source and adjusting Ph, and PHAs is accumulated in a circular and intermittent aeration method of aeration, aeration stopping and stirring.
Description
Technical field
The present invention relates to the compound method of a kind of Biodegradable material polyhydroxyalkanoate (PHAs), especially relate to a kind of method of utilizing residual active sludge biosynthesizing polyhydroxyalkanoate.
Background technology
Adopt microorganisms producing degradable plastics polyhydroxyalkanoate (PHAs) after oil crisis in 1970 is carried out with movement of environmental protection, just to receive attention widely.PHAs has a wide range of applications in fields such as medicine, organizational project, plastics and piezoelectric article because of its unique physico-chemical property with biocompatibility and biodegradability.At present, the research of biosynthesizing PHAs has been become heat subject, some countries have carried out the suitability for industrialized production of fermentation using bacteria PHAs.Although comparatively abundant to the research of sterile fermentation method both at home and abroad at present, Technology is also comparatively ripe, and production cost is high, compares price with conventional plastic and exceeds 3～5 times, and can not obtain large-scale industrial application always.Many bacteriums in the excess sludge can absorb organism accumulation PHAs under the unbalanced growth conditions of nutritive substance, its abundant mixed bacterial is less demanding to the processing condition of synthetic PHAs, is the effective way of low cost prodn PHAs.Like (Water Science and Technology, 1998,38 such as Satoh; 103-109) reported and utilized excess sludge, little aerobic-aerobic processing condition under, the semi-invariant of PHAs is higher; Can reach 62% of mud mixed liquid suspended sediment concentration (MLSS), but cumulative time is longer, is 30h; And the very difficult control of microaerophilic processing condition, to realizing that industriallization exerts a certain influence.Publication number is that to disclose a kind of be raw material with the active sludge in the application for a patent for invention of CN101235400; Utilize genetic engineering bacterium to produce the method for PHAs; The voltaile fatty acid that this method is produced with the sludge hydrolytic acidifying is a carbon source, utilizes genetic engineering bacterium to carry out the synthetic of PHAs, can reach the purpose of sludge reduction; Behind accumulation 60h, the content of PHAs can account for 65% of dried cell weight; But this method belongs to sterile fermentation (according to pertinent literature, the content of the synthetic PHAs of sterile fermentation can account for dried cell weight more than 90%), and semi-invariant is not high comparatively speaking, and cumulative time is longer.Publication number is that the application for a patent for invention of CN1786147 discloses a small amount of indigenous PHAs high yield synthesis bacterium of a kind of employing re-injection, utilizes self-control sludge acclimatization device, under 25 ℃; Adopt the 2h anaerobism, 4h is aerobic, comprises that draining changes the domestication mode of each domestication circulation 8h of water; The domestication direction of " regulation " domestication initial activity mud is implemented 3 circulations every day, and whole acclimation period is 10 days; Impel that the PHAs synthesis bacterium becomes dominant microflora in the active sludge, improve the synthetic PHAs productive rate of active sludge; In temperature is 30 ℃, can improve 51.9% of the synthetic PHAs productive rate of active sludge behind the accumulation 48h effectively, but this method sludge acclimatization complicated condition, and the PHAs cumulative time is longer.(Bioresource Technology, 2009,100 such as Cai Mengmeng; 1399-1405) reported that the voltaile fatty acid that utilizes excess sludge to produce is the synthetic PHAs of carbon source, mud is without domestication, at room temperature; Stirring velocity is 250r/min; Aeration rate is 1L/Lmin, does not control under the condition of pH value, and the PHAs semi-invariant accounts for 56.5% of dried cell weight; This method is a carbon source with the lipid acid that mud produces, and can reduce the synthetic cost of PHAs, but the PHAs semi-invariant is not high, and acid process operation in early stage more complicated.(Biomass andBioenergy, 2009,33 such as Chen Hong; 721-727) reported the condition optimizing that utilizes the synthetic PHAs of excess sludge; Adopt aerobic instantaneous feed method, be 9.0 in original ph, C: N is that 60: 1, magneticstrength are under the 11mT condition, the PHAs semi-invariant accounts for dried cell weight 49.5%; But its domestication was for up to two months, and the PHAs semi-invariant is lower.
Although above-mentioned patent, document are inquired into and studied the technology of mud synthesizing polyhydroxyalkanoateby, utilize the productive rate of mud synthesizing polyhydroxyalkanoateby and cumulative time all not to reach industrial requirement at present.
Summary of the invention
The object of the invention aims to provide a kind of large-scale industrial production that is applicable to, and is simple in structure, easy to operate, the reaction unit of cheap sludge acclimatization and mud synthesizing polyhydroxyalkanoateby.
Another object of the present invention provides a kind of reaction unit that adopts said sludge acclimatization and mud synthesizing polyhydroxyalkanoateby, the method for sludge acclimatization that the mud synthetic yield is higher and mud synthesizing polyhydroxyalkanoateby.
The reaction unit of sludge acclimatization according to the invention and mud synthesizing polyhydroxyalkanoateby comprises sludge acclimatization device and synthesis reactor.
Said sludge acclimatization device is provided with domestication retort and domestication reaction aeration head; Domestication reaction aeration head places the bottom of domestication retort; The inlet mouth of domestication reaction aeration head is connected with spinner-type flowmeter and the air of being located at domestication retort outside through pipe connecting; The aeration rate of domestication reaction aeration head is controlled by spinner-type flowmeter, and the tank skin of domestication retort is provided with at least 1 mud discharging mouth that is used for the draining spoil disposal;
Synthesis reactor is provided with constant temperature water bath, building-up reactions jar, 2 ASIC micro computer time controllers, building-up reactions aeration head and whisking appliances; The building-up reactions jar places in the constant temperature water bath; Building-up reactions aeration head and whisking appliance place the building-up reactions pot bottom; The inlet mouth of building-up reactions aeration head is connected with spinner-type flowmeter and the air of being located at the outside through pipe connecting, and 2 ASIC micro computer time controllers are connected with air with whisking appliance respectively, are used to control the time of aeration and stirring.
The method of said sludge acclimatization and mud synthesizing polyhydroxyalkanoateby may further comprise the steps:
1) getting active sludge drops in the domestication retort of sludge acclimatization device; Control aeration rate 1～3L/L/min;------spoil disposal---deposition---water outlet is that 1 acclimation period is tamed to aerobic aeration, in 10～15 cycles of continuous domestication, obtains taming stable mud by water inlet;
2) getting the stable mud of domestication in the building-up reactions jar of synthesis reactor, is carbon source with acetate, and adjust pH is 5.0～11.0, and the circular gap aeration mode accumulation PHAs 6～18h of the stirring that---stops exposing to the sun---by aeration gets polyhydroxyalkanoate.
In step 1), the sludge concentration of said active sludge (MLSS) is preferably 1～4g/L, and the said active sludge of getting drops in the domestication retort of sludge acclimatization device, preferably regulates pH 5.0～9.0; Said 1 acclimation period is preferably 20～24h, and the time of said aerobic aeration is preferably 19～23h, and the said sedimentary time is preferably 20～30min, row's supernatant; Said water is preferably culture medium solution, and composition in every 1L culture medium solution and the concentration in the domestication reaction system are: CH
3COOH0.4～1.2mg/L, KCl 117～351mg/L, K
2HPO
43H
2O 75～225mg/L, NH
4Cl 97～291mg/L, MgSO
475～225mg/L, CaCl
227～81mg/L, FeCl
36H
2O 5～15mg/L, peptone 167～501mg/L, yeast extract paste 62～186mg/L; Said spoil disposal is for discharging the mud of growth, and is constant with the sludge concentration in the control domestication retort.
In step 2) in, the temperature in the said building-up reactions jar is preferably 20～35 ℃; The process of said aeration is preferably aeration 15～60min, stops the 15～60min that exposes to the sun, and opens mechanical stirring when stopping exposing to the sun, and the aeration rate of said aeration is preferably 1～3L/L/min; The speed of said stirring is preferably 200～500r/min; The volume by volume concentration of said acetate in the building-up reactions system is preferably 2.5～6.0mL/L.
Because the present invention adopts the reaction unit of sludge acclimatization and mud synthesizing polyhydroxyalkanoateby, sludge acclimatization and the synthetic PHAs of mud are combined, so required equipment is simple in structure, easy to operate, cheap.In addition, the sludge acclimatization process condition is simple, control easily, and PHAs building-up process cumulative time is short, and the productive rate of PHAs is applicable to the large-scale industrial production of PHAs up to 67.0% (PHAs/MLSS).
Description of drawings
Fig. 1 is the structural representation of the sludge acclimatization device of the reaction unit of domestication of embodiment of the invention mud and mud synthesizing polyhydroxyalkanoateby.
Fig. 2 is the structural representation of the synthesis reactor of the reaction unit of domestication of embodiment of the invention mud and mud synthesizing polyhydroxyalkanoateby.
Embodiment
Following examples will combine accompanying drawing that the present invention is described further.
Embodiment 1
The reaction unit of sludge acclimatization according to the invention and mud synthesizing polyhydroxyalkanoateby comprises sludge acclimatization device and synthesis reactor.
Said sludge acclimatization device is provided with domestication retort 3 and domestication reaction aeration head 4; Domestication reaction aeration head 4 places the bottom of domestication retort 3; The inlet mouth of domestication reaction aeration head 4 is connected with spinner-type flowmeter 2 and the air 1 of being located at domestication retort 3 outsides through pipe connecting, and the aeration rate of domestication reaction aeration head 4 is by spinner-type flowmeter 2 controls, and the cubic capacity of domestication retort 3 is 6L; Domestication reaction aeration head 4 adopts the core aeration head; Every from the bottom to top 1L place establishes the mud discharging mouth 31 of a band valve on the tank skin of domestication retort 3, and the mud discharging mouth of 5 band valves is set altogether, is used for the draining spoil disposal.
Synthesis reactor is provided with constant temperature water bath 5, building- up reactions jar 6,2 ASIC micro computer time controllers 9 and 12, building-up reactions aeration head 8 and whisking appliances 7; Building-up reactions jar 6 places in the constant temperature water bath 5; Building-up reactions aeration head 8 places building-up reactions jar 6 bottoms with whisking appliance 7; The inlet mouth of building-up reactions aeration head 8 is connected with spinner-type flowmeter 10 and the air 11 of being located at the outside through pipe connecting; 2 ASIC micro computer time controllers 9 are connected with air 11 with whisking appliance 7 respectively with 12, are used to control the time of aeration and stirring.
Getting 5L MLSS is the domestication retort of the active sludge input sludge acclimatization device of 2g/L, adds with CH
3COOH 0.75mL/L, KCl 234mg/L, K
2HPO
43H
2O 150mg/L, NH
4Cl 194mg/L, MgSO
4150mg/L, CaCl
254mg/L, FeCl
36H
2O 10mg/L, peptone 334mg/L, the culture medium solution that yeast extract paste 124mg/L is mixed with; Adjust pH is 5.0, is 2L/L/min by spinner-type flowmeter control aeration rate, aerobic aeration 23h; Stop aeration, open the mud discharging mouth spoil disposal, sludge concentration is 2g/L in the control domestication retort; Discharge the 3L supernatant behind the deposition 30min, and again " water inlet---aerobic aeration---spoil disposal---deposition---water outlet " cultivate 13 all after dates of domestication, sludge character is stable; Outward appearance is changed into light brown gradually by black, SVI (SVI) is 105mL/g.
The sophisticated mud 1L of domestication is imported through pipe in the building-up reactions jar of synthesis reactor, regulate constant temperature water bath under 30 ℃, add the acetate of 4.5mL/L; Control pH value is 6.0, aeration rate 2L//L/min, stirring velocity 400r/min; By " aeration 30min stirs 30min; Open to stir when stopping exposing to the sun " the circular gap aeration mode to carry out the mud of PHAs synthetic, accumulative total is after 13 hours, PHAs content 2.5g/L, PHAs/MLSS 66.0%.
Change different acetate consumptions and synthesize with the mud that different pH values is carried out PHAs, all the other methods and condition are with embodiment 1, and the result of mud accumulation PHAs sees table 1.
The different carbon source consumptions of table 1, pH the value significant parameter of mud accumulation PHAs down compare
Press embodiment 1 method, get the active sludge that 5L MLSS is 1g/L, add with CH
3COOH 0.4mL/L, KCl117mg/L, K
2HPO
43H
2O 75mg/L, NH
4Cl 97mg/L, MgSO
475mg/L, CaCl
227mg/L, FeCl
36H
2O5mg/L, peptone 167mg/L, the substratum that yeast extract paste 62mg/L is mixed with; Adjust pH is 7.0, and aeration rate is 1L/L/min, behind the aeration 19h; Stop aeration, open the mud discharging mouth spoil disposal, sludge concentration is 1g/L in the control domestication retort; Discharge the 3L supernatant behind the deposition 20min, 1 cycle is 20h; Again " water inlet---aerobic aeration---spoil disposal---deposition---water outlet " cultivate domestication 11 all after dates, sludge character is stable, and outward appearance is changed into light brown gradually by black, and SVI (SVI) is 108mL/g.
PHAs compound method with the sophisticated mud 1L of domestication presses embodiment 1 adds 1.5mL/L acetate, control aeration rate 1L//L/min, and (aeration 15min stirs 15min to stir speed (S.S.) 200r/min; Open when stopping exposing to the sun and stir), the pH value is 5.0, and temperature of reaction is 20 ℃, and accumulative total is after 6 hours, and PHAs content 0.4g/L, PHAs/MLSS are 28.9%.
Embodiment 8
Press embodiment 1 method, getting 5L MLSS is the domestication retort of the active sludge input sludge acclimatization device of 2g/L, adds with CH
3COOH 0.75mL/L, KCl 234mg/L, K
2HPO
43H
2O 150mg/L, NH
4Cl 194mg/L, MgSO
4150mg/L, CaCl
254mg/L, FeCl
36H
2O 10mg/L, peptone 334mg/L, the substratum that yeast extract paste 124mg/L is mixed with; Adjust pH is 9.0, is 2L/L/min by spinner-type flowmeter control aeration rate, behind the aerobic aeration 23h; Stop aeration, open the mud discharging mouth spoil disposal, sludge concentration is 2g/L in the control domestication retort; Discharge the 3L supernatant behind the deposition 30min, one-period is 24h; " water inlet-aerobic aeration-spoil disposal-deposition-water outlet " cultivated 10 all after dates of domestication again, and sludge character is stable, and outward appearance is changed into light brown gradually by black, and SVI (SVI) is 102mL/g.
Embodiment 9～12:
Adopt the sophisticated mud 1L of domestication among the embodiment 8, the PHAs compound method of pressing embodiment 1 adds 4.5mL/L acetate, and the mud that adopts different pH values to carry out PHAs synthesizes, and other condition is aeration 2L/L/min, and (aeration 30min stirs 30min to stir 400r/m; Open when stopping exposing to the sun and stir).The different pH values result of mud accumulation PHAs are down seen table 2.
The different pH values of table 2 significant parameter of mud accumulation PHAs down compare
Embodiment 13
Press embodiment 1 method, get the active sludge that 5L MLSS is 3g/L, add with CH
3COOH 1.2mL/L, KCl351mg/L, K
2HPO
43H
2O 225mg/L, NH
4Cl 291mg/L, MgSO
4225mg/L, CaCl
281mg/L, FeCl
36H
2O15mg/L, peptone 501mg/L, the substratum that yeast extract paste 186mg/L is mixed with; Adjust pH is 11.0, and aeration rate is 3L/L/min, behind the aerobic aeration 23h; Stop aeration, open the mud discharging mouth spoil disposal, sludge concentration is 2g/L in the control domestication retort; Discharge the 3L supernatant behind the deposition 30min, one-period is 24h; Again " water inlet---aerobic aeration---spoil disposal---deposition---water outlet " cultivate domestication 15 all after dates, sludge character is stable, and outward appearance is changed into light brown gradually by black, and SVI (SVI) is 106mL/g.
Just tame the PHAs compound method of sophisticated mud, add 6.0mL/L acetate by embodiment 1, control aeration rate 3L//L/min, (aeration 60min stirs 60min to stir speed (S.S.) 500r/min; Open when stopping exposing to the sun and stir), the pH value is 11.0, and temperature of reaction is 35 ℃, and behind the accumulative total 14h, PHAs content is 2.2g/L, and PHAs/MLSS is 52.6%.
Claims (6)
1. the method for sludge acclimatization and mud synthesizing polyhydroxyalkanoateby; It is characterized in that; Adopt the reaction unit of a kind of sludge acclimatization and mud synthesizing polyhydroxyalkanoateby, the reaction unit of said a kind of sludge acclimatization and mud synthesizing polyhydroxyalkanoateby comprises sludge acclimatization device and synthesis reactor;
Said sludge acclimatization device is provided with domestication retort and domestication reaction aeration head; Domestication reaction aeration head places the bottom of domestication retort; The inlet mouth of domestication reaction aeration head is connected with spinner-type flowmeter and the air of being located at domestication retort outside through pipe connecting; The aeration rate of domestication reaction aeration head is controlled by spinner-type flowmeter, and the tank skin of domestication retort is provided with at least 1 mud discharging mouth that is used for the draining spoil disposal;
Synthesis reactor is provided with constant temperature water bath, building-up reactions jar, 2 ASIC micro computer time controllers, building-up reactions aeration head and whisking appliances; The building-up reactions jar places in the constant temperature water bath; Building-up reactions aeration head and whisking appliance place the building-up reactions pot bottom; The inlet mouth of building-up reactions aeration head is connected with spinner-type flowmeter and the air of being located at the outside through pipe connecting, and 2 ASIC micro computer time controllers are connected with air with whisking appliance respectively, are used to control the time of aeration and stirring;
Said method comprising the steps of:
1) getting active sludge drops in the domestication retort of sludge acclimatization device; Control aeration rate 1～3L/L/min,------spoil disposal---deposition---water outlet is that 1 acclimation period is tamed to aerobic aeration, 10～15 cycles of continuous domestication by water inlet; Obtain taming stable mud; The time of said aerobic aeration is 19～23h, and the said sedimentary time is 20～30min, row's supernatant;
During said water inlet, be to add with CH
3COOH 0.4～1.2mg/L, KCl 117～351mg/L, K
2HPO
43H
2O 75～225mg/L, NH
4Cl 97～291mg/L, MgSO
475～225mg/L, CaCl
227～81mg/L, FeCl
36H
2O 5～15mg/L, peptone 167～501mg/L, the culture medium solution that yeast extract paste 62～186mg/L is mixed with;
2) get the stable mud of domestication in the building-up reactions jar of synthesis reactor; With acetate is carbon source; Adjust pH is 5.0～11.0;---stop exposing to the sun---by the aeration circular gap aeration mode accumulation PHAs 6～18h of stirring, polyhydroxyalkanoate, the temperature in the said building-up reactions jar is 20～35 ℃; The process of said aeration is aeration 15～60min, stops the 15～60min that exposes to the sun, and opens mechanical stirring when stopping exposing to the sun, and the aeration rate of said aeration is 1～3L/L/min.
2. the method for sludge acclimatization as claimed in claim 1 and mud synthesizing polyhydroxyalkanoateby is characterized in that in step 1), and the sludge concentration of said active sludge is 1～4g/L.
3. the method for sludge acclimatization as claimed in claim 1 and mud synthesizing polyhydroxyalkanoateby is characterized in that in step 1), and the said active sludge of getting drops in the domestication retort of sludge acclimatization device, regulates pH 5.0～9.0.
4. the method for sludge acclimatization as claimed in claim 1 and mud synthesizing polyhydroxyalkanoateby is characterized in that in step 1), and said 1 acclimation period is 20～24h.
5. the method for sludge acclimatization as claimed in claim 1 and mud synthesizing polyhydroxyalkanoateby is characterized in that in step 2) in, the speed of said stirring is 200～500r/min.
6. the method for sludge acclimatization as claimed in claim 1 and mud synthesizing polyhydroxyalkanoateby is characterized in that in step 2) in, the volume by volume concentration of said acetate in the building-up reactions system is 2.5～6.0mL/L.
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| CN103087897A (en) * | 2011-11-01 | 2013-05-08 | 天津农学院 | Microbial gum fermentation broth bacterium-gum separation method and device |
| CN102505025B (en) * | 2011-12-02 | 2014-09-24 | 厦门大学 | Method for synthesizing polyhydroxyalkanoate by using residual sludge broth as substrate |
| CN104561144A (en) * | 2015-01-09 | 2015-04-29 | 厦门大学 | Method for producing medium-chain-length polyhydroxyalkanoates by virtue of excess activated sludge |
| CN106186619B (en) * | 2016-08-17 | 2019-11-19 | 三明学院 | A kind of method of sludge organism synthesis of hydroxy butyric acid and Hydroxyoctanoic acid copolymer |
| CN108641973A (en) * | 2018-04-03 | 2018-10-12 | 中海石油(中国)有限公司湛江分公司 | One plant of marine bacteria for producing polyhydroxyalkanoates and its application |
| CN109250811A (en) * | 2018-10-08 | 2019-01-22 | 广州资源环保科技股份有限公司 | A kind of automatic domesticating device of activated sludge and its method for preparing activated sludge |
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