CN101549932B - Integrated production method of organic sewage/waste residue treatment, microalgae culturing and oil refining - Google Patents
Integrated production method of organic sewage/waste residue treatment, microalgae culturing and oil refining Download PDFInfo
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- CN101549932B CN101549932B CN2009100511523A CN200910051152A CN101549932B CN 101549932 B CN101549932 B CN 101549932B CN 2009100511523 A CN2009100511523 A CN 2009100511523A CN 200910051152 A CN200910051152 A CN 200910051152A CN 101549932 B CN101549932 B CN 101549932B
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Micro-Organisms Or Cultivation Processes Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention relates to the environmental protection field, the microalgae cultivation engineering field and the biodiesel refining field, specifically an integrated production method of organic sewage/waste residue treatment, microalgae culturing and oil refining. The method comprises: treating the organic sewage and organic waste residue respectively by anaerobic biochemical technology to generate biogas for generating electricity and supplying heat; performing aerobic biochemical treatment to the sewage and biogas slurry; blending into nutrient solution, and adding into large-scale photobioreactor; passing into biogas, burning to generate carbon dioxide waste gas for culturing oil-containing microalgae; collecting the obtained microalgae by air floatation method and breaking the walls;separating the oil-containing microalgae into microalgae oil, microalgae protein, microalgae polysaccharide and microalgae residue; and refining biodiesel accorded with the national standard using th e microalgae oil as raw oil. The invention integrates the organic sewage and waste residue treatment, microalgae culturing and processing, and biodiesel refining; reduces production cost; realizes biodiesel clean production; and treats the 'three wastes'.
Description
[technical field]
The present invention relates to environmental protection field, little algae culturing engineering field, biological diesel oil refining field, specifically a kind of production method of organic sewage waste residue treatment, microalgae culturing and oil refining.
[background technology]
Current global energy crisis increasingly sharpens, and spreading unchecked of eutrophication water becomes environmental hazard, and carbonic acid gas excessively discharges and the Greenhouse effect that cause have produced serious climate disaster, and the environmental protection situation is very severe.Body eutrophication is meant the too much caused water pollution phenomenons of plant nutrient substance content such as nitrogen, phosphorus.These supernutrition materials mainly come from the sanitary sewage in city and rural area, and organic sewage that produces in the industrial and agricultural production and organic waste residues, plant particularly, the slaughterhouse, meat packing plant, aquatic products processing factory, corn processed factory, potato source mill, fruits and vegetables canning factory, food processing plant etc., and bean product, milk-product, wine, sugar, beverage, cold drink, alcohol, grease, starch, monosodium glutamate, soy sauce, vinegar, yeast, pickles, citric acid, lactic acid, Yeast Nucleic Acid, the production of products such as coffee, the capital produces a large amount of organic sewage and organic waste residues, and stalk, leaf, weeds, ight soil etc. are the ubiquitous organic waste residues in rural area.
For example, the vinasse sewage of Alcohol Production discharging is a kind of high density, high-temperature, high suspended matter, silt is many, viscosity is big, be the tart organic sewage, mainly contains organic waste residues such as remaining starch, Mierocrystalline cellulose, crude protein and mycoprotein in the sewage.And for example, since the seventies in 20th century, China's aquaculture trends towards intensifying, the aquaculture model of batch production, high-density, high production, this high-density breeding pattern has improved the scale and the output of aquaculture effectively, but the movement of cultivated animals is deposited in the water with the bait residue that is rich in high protein, makes water quality deterioration.In order to keep the quality of aquaculture water, the concentration of objectionable impurities is diluted or reduced to the method that water is frequently changed in normal employing in the production, especially arrived the breed later stage, and quantity of wastewater effluent increases severely, not only caused water resource waste, and a large amount of nutritive salt has also caused pollution near waters in its sewage.China does not still have the relevant policy rules to the discharging of aquaculture wastewater, the careless mostly discharging of aquaculture wastewater, even the adjacent water-in of breed pond water port that has, and secondary pollution is quite serious.Therefore, purify and utilize aquaculture wastewater to become the key link of culture fishery Sustainable development.
At present, remove the traditional sewage biochemical processing of the still many employings of organism in the sewage,, reduce BOD, COD, still contain nutritive substances such as more nitrogen, phosphorus in the water outlet, cause body eutrophication easily though this method can be removed partial organic substances in the sewage.Because organic sewage and organic waste residues biodegradability are stronger, have the potential resource and can utilize characteristic.The substratum that foodstuffs industry sewage can be used as on the biological significance is cultured spirulina, and this respect has had some successful examples, and nutritive substances such as the nitrogen in the sewage, phosphorus have also obtained removal to a certain extent.For example, Milk Products Plant sewage be through can being used for the cultivation of spirulina after suitably handling, and experimental result shows, can not add any nutritive ingredient in sewage and realizes that the full sewage of spirulina cultivates.With the organic sewage is that nutrition source is cultivated the feed grade spirulina, the ecological circulation that helps organic waste materials becomes the high-quality protein feed of harmful sewage into high value, can effectively solve feedstuff protein source shortage problem, reduce aquaculture cost, and can improve the meat of aquatic animal.
Biofuel is a fatty acid methyl ester, it is the most potential clean reproducible energy product that substitutes petrifaction diesel that becomes, it has good environmental-protecting performance, good safety performance, good combustionproperty, lubricity etc., and biofuel itself preferably still a kind of excellent solvent and important chemical material.The key of development biofuel is the supply of raw oil material; therefore; thereby adopt cheap glyceride stock and raising grease transformation efficiency to reduce cost; be biofuel whether can mass-producing, the key of industrialization, choose suitable, oil resource produces the general trend that thing diesel oil is development next life cheaply.As everyone knows, characteristics such as algae has the photosynthetic efficiency height, adaptive capacity to environment is strong, growth cycle is short, biological yield height, therefore, the oil-containing algae is the good raw material of preparation biofuel.With " engineering microalgae " production biofuel, for diesel production has been opened up a new technological approaches.Utilize organic sewage and organic waste residues and CO 2 waste gas to cultivate oil-containing micro-algae for main raw material; from little algae, extract little algae oil then; and be stock oil production biofuel with little algae oil; can reduce the production cost of biofuel significantly; therefore, " pollution treatment-support algae-oil refining " become one of solution global energy crisis and the most promising approach of environmental pollution.
[summary of the invention]
The present invention utilizes anaerobic biological technical point other places reason organic sewage and organic waste residues, producing biogas generates electricity, heat supply, again sewage and natural pond liquid are carried out after aerobic biochemical handles, be deployed into nutrient solution, join in the large-scale bioreactor, and the CO 2 waste gas that feeds biogas burning back generation is cultured oil-containing micro-algae, be stock oil refining biofuel with little algae oil then, a kind of production method of organic sewage waste residue treatment, microalgae culturing and oil refining is proposed thus, comprise equalizing tank, anaerobic biochemical reactor, the aerobic biochemical reactor, disinfection tank, the stack retting pond, digester, thionizer, gas holder, the power generation and heat supply device, the nutrient solution blend tank, Erlenmeyer flask, airlift photobioreactor, small-sized gas push type photobioreactor, large-scale gas push type photobioreactor, air flotation tank, high pressure homogenizer, horizontal spiral centrifuge, water-and-oil separator, the vacuum concentration still, the still of saltouing, the high speed centrifugation filter, moisture eliminator, the alcohol precipitation still, the ethanol recovery tower, multifunctional reaction still, skimmer, methanol distillation column, the methyl alcohol basin, water washing tank, distillation tower, equipment such as biofuel basin is characterized in that may further comprise the steps:
A. the processing of organic sewage waste residue
Organic sewage enters equalizing tank after grid is removed than mechanical impuritys such as big floating matters, regulate the sewage water yield, water quality, pH value, enters then to carry out the anaerobic biological processing in the anaerobic biochemical reactor.The mud that organic waste residues produces with anaerobic biochemical reactor adds the stack retting pond and carries out pile fermentation, material behind stack retting joins in the digester (methane-generating pit) and carries out anaerobically fermenting, and the mud that aerobic biochemical reactor is produced joins in the digester in the lump simultaneously.During anaerobically fermenting, the carbon-nitrogen ratio of raw material is (20～30): 1, and solid content is 5%～45% (weight ratio), the fermentation back produces biogas, natural pond slag and natural pond liquid.The natural pond slag is as fertilizer, and natural pond liquid joins anaerobic biochemical reactor and carries out the anaerobic biological processing again.The biogas that biogas that digester produces and anaerobic biochemical reactor produce enters thionizer in the lump and collect gas holder after desulfurization, is used for power generation and heat supply.Organic sewage and natural pond liquid are after anaerobic biochemical reactor is handled, join again and carry out the aerobic biochemical processing in the aerobic biochemical reactor, further reduce BOD, the COD of organic sewage and natural pond liquid, and ammonia nitrogen is converted into ammonium salt, nitrate or the nitrite that is absorbed by little algae easily, eliminate the peculiar smell of organic sewage and natural pond liquid simultaneously.Organic sewage and natural pond liquid after aerobic biochemical is handled enter in the disinfection tank after filtering, adding sterilizing agent carries out disinfection, kill wherein virus, bacterium, fungi, protozoon and assorted algae, add in the neutralizing agent then and thimerosal, join at last in the nutrient solution blend tank and cultivate main nitrogenous source and phosphorus source as little algae;
B. marsh gas power generation heat supply
The power generation and heat supply device that is adopted among the present invention is array mode or the array mode of biogas-diesel motor generating set and waste heat boiler or the array mode of gas-turbine generator set and waste heat boiler and steam turbine generating set of gas fuel boiler and steam turbine generating set.The used fuel of power generation and heat supply device is mainly biogas and coarse biodiesel.Power generation and heat supply device electricity is used for the processing of organic sewage waste residue, little algae cultivation and processing, biological diesel oil refining, power generation assembly itself and office household electricity, Low Temperature Steam that is produced and hot water are used for little algae cultivation and processing, biological diesel oil refining, digester and anaerobic biochemical reactor insulation and office life with hot, and insufficient thermoelectricity is by mains supply, heating network heat supply.The stack gas that is rich in carbonic acid gas that the power generation and heat supply device produces feeds large-scale gas push type photobioreactor after purifying, as the main carbon source that little algae is cultivated, insufficient carbon source is by liquid carbon dioxide that adds or sodium bicarbonate supply;
C. utilize carbonic acid gas stack gas, organic sewage and the cultivation of natural pond liquid and gather little algae
At first the algae kind is successively carried out three grades of expanding species in Erlenmeyer flask, airlift photobioreactor, small-sized gas push type photobioreactor and cultivate, make industrial production algae kind as industrial production device; Industrial production device is to place the outdoor large-scale gas push type photobioreactor that is arranged in parallel by row and row, adding nutrient solution earlier in reactor makes liquid level reach 10 centimetres, the main body of starting breather generation nutrient solution then flows, inoculate above-mentioned industrial production algae kind subsequently, and progressively add nutrient solution and make liquid level reach 20 centimetres, feed continuously by day carbon dioxide content after filtration air be diluted to 1%～5% carbonic acid gas stack gas, to guarantee the growth of little algae, feed filtrated air at night and keep the breathing of little algae, adopt logical hot/cold wind, ventilation puts in a skylight, the shading temperature adjustment, means such as steam/heat water insulation are controlled at 15～35 ℃ with the temperature of nutrient solution; After detecting the nutrient minimizing or the decline of algae liquid liquid level in the nutrient solution, carry out fluid infusion by liquid supplementation pipe, the highest liquid level after the fluid infusion is 30 centimetres; Look micro algae culturing liquid concentration little algae of irregularly gathering, promptly open the liquid discharge pipe valve and discharge algae liquid, when the liquid level of large-scale gas push type photobioreactor is reduced to 15～20 centimetres, stop discharge opeing, to control each recovery ratio 10%～30%; Gathering of little algae adopts the aerating collecting method that feeds carbonic acid gas stack gas in air flotation tank to carry out, and realizes the carbonic acid gas of complement lysis in micro algae culturing liquid simultaneously;
D. the full use of oil-containing micro-algae
Little algae (slurry) that aerating collecting obtains adopts horizontal spiral centrifuge to carry out liquid-solid separation behind the high pressure homogenizer broken wall, and isolated little algae-residue is used to produce little algae composite fertilizer.Isolated liquid phase is added to and is separated into oil phase and water in the water-and-oil separator, and oil phase is little algae oil.The water material is added in the vacuum concentration still, and thickening temperature is made as 60～70 ℃, and concentration time was made as 1～2 hour.Material after concentrating enters the still of saltouing, and according to the volume of material, the saturation computation ammonium sulfate consumption by 30%～50% slowly is added to solid ammonium sulfate in the still of saltouing, and fully stirs, and precipitates little algae albumen, and the time of saltouing was made as 2～5 hours.Material after saltouing carries out liquid-solid separation with the high speed centrifugation filter, and isolated solid phase is added to carries out drying and make little algae albumen in the moisture eliminator.Isolated liquid phase is added in the alcohol precipitation still, extract little polysaccharides with ethanol precipitation, promptly slowly add concentration and be 70%～95% industrial alcohol under whipped state and carry out alcohol precipitation, the volume ratio of industrial alcohol add-on and original solution is made as 2～4: 1, and the alcohol precipitation time of repose was made as 3～12 hours.Material behind the alcohol precipitation carries out liquid-solid separation with the high speed centrifugation filter, and isolated liquid phase is added to carries out rectifying in the ethanol recovery tower, and overhead product is the ethanol of 70%～95% concentration, and bottom product is little algae liquid fertilizer, as the foliar nutrient of plant; Isolated solid phase then is added to carries out drying and makes little polysaccharides in the moisture eliminator;
The pre-treatment of e. little algae oil and transesterification reaction
The equipment of the pre-treatment of little algae oil and refining biofuel thereof adopts multifunctional reaction still, in multifunctional reaction still, add algae oil in a subtle way, carry out vacuum hydro-extraction earlier, add the methyl alcohol and the vitriol oil then and carry out pre-esterification reactor, make the free fatty acids in the stock oil turn to fatty acid methyl ester, after pre-esterification reactor finishes, according to added vitriol oil amount, calculate the amount of the required sodium hydroxide that just in time neutralizes fully, in reactor, add the sodium hydroxide saturated solution for preparing and carry out neutralization reaction, after reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize dehydration, separating methanol, methyl alcohol by rectifying and water sepn after reuse; After the pre-treatment of little algae oil finishes, in multifunctional reaction still, add methyl alcohol and alkaline catalysts sodium hydroxide, carry out transesterification reaction, make the glycerin fatty acid ester reaction in the stock oil generate fatty acid methyl ester, after transesterification reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize separating methanol, direct reuse after methyl alcohol is condensed; Behind the vacuum separating methanol, from multifunctional reaction still, discharge the mixture of product fatty acid methyl ester and by-product glycerin, then by after skimmer standing demix or the centrifugation, crude fatty acid methyl ester (coarse biodiesel) is washed and distill, make the biofuel of national standards such as meeting China or Germany; One of carbon source that in the isolated raw glycerine 10%～70% cultivated as little algae is added in the micro algae culturing liquid blend tank, and remaining raw glycerine is further refining; To the sodium hydroxide sewage that produces in the coarse biodiesel water washing process absorption agent, absorb the nutritive salt that sodium bicarbonate that the back produces is cultivated as little algae as carbonic acid gas; Sodium hydroxide sewage is added in the air flotation tank, heightens the pH value of algae liquid, helps flocculation and the air supporting of little algae; Sodium hydroxide sewage is added in the nutrient solution blend tank, regulates the pH value of nutrient solution, makes it to be more suitable for the growth of little algae; The waste salt that in the vitriol oil and the sodium hydroxide and back generates is added in the nutrient solution blend tank, becomes salinity source and nutritive salt that the little algae of salt water is cultivated.
Among the present invention, described anaerobic biochemical reactor is common anaerobic digester, up flow anaerobic sludge blanket reactor (UASB), internal-circulation anaerobic reactor (IC), CGSB (EGSB), outer circulation anaerobic reactor (EC), flow lifting type anaerobism solid reactor (USR), anaerobic baffled reactor (ABR), upflow anaerobic sludge blanket process-filtering layer reactor (UBF), anaerobic biofilter (AF), hybrid anaerobic reactor (AHR), anaerobic batch reactor (ASBR), anaerobic expanded bed bioreactor (AEBR), anaerobic fluidized bed reactor (AFBR), anaerobism pulling flow type fixed-bed reactor, anaerobe rotating disk (ARBC), anaerobism flow lifting type fluidized-bed reactor (UFB Biobed), anaerobic composite bed reactor (AF+UASB), vertical baffling anaerobic mud bed reactor etc.
Described aerobic biochemical reactor be active sludge aeration tank, BAF, aerobic biofilter, biological contact oxidation pond, oxidation ditch, oxidation pond, CASS aerobic biochemical pond, sbr reactor pond, aerobic biological fluid-bed, drip filter bed, aerobe rotating disk etc.
Described sterilizing agent is ozone or dioxide peroxide or ultraviolet ray.Neutralizing agent adopts Sulfothiorine.
Described little algae is adopted freshwater microalgae or little algae of salty lake water or the little algae of seawater, and classification is chrysophyceae or green alga or diatom or blue-green algae or red algae, is preferably to contain the high salt algae of fat or chlorella or Isochrysis galbana 3011 or pavlova viridis.
Described moisture eliminator is lyophilizer or spray-dryer.
[description of drawings]
Fig. 1 is the production scheme of organic sewage waste residue treatment, microalgae culturing and oil refining.
[embodiment]
The invention will be further described below in conjunction with embodiment that accompanying drawing and accompanying drawing provide.Production technology of the present invention is to implement easily to this professional people.
Build waste disposal plant and large methane tank, both culturing microalgae processing space and biological diesel oil refining factory the year deliver the large-scale pig farms of 100,000 pigs for sale in a family near, adopt and handle the production method that algae oil refining is supported in organic sewage waste residue (mainly comprising pig farm ight soil, urine, sewage, near stalk etc.) coupling, production biofuel, little algae albumen, little polysaccharides, little algae fertilizer etc. are referring to Fig. 1.
Liquid dung that the pig farm is collected and flushing sewage enter equalizing tank after grid is removed than mechanical impuritys such as big floating matters, regulate the sewage water yield, water quality, pH value, enter then and carry out anaerobic biological in 1700 cubic metres the up flow anaerobic sludge blanket reactor (UASB) and handle, this anaerobic biochemical reactor day is disposed of sewage 850 cubic metres, on average produces 500 cubic metres of biogas daily.The mud that pig manure that the pig farm is collected and the dry rice straw through shredding produce with the UASB reactor adds the stack retting pond and carries out pile fermentation, the mud that material behind stack retting and BAF produce joins in the lump in 5000 cubic metres the digester and carries out anaerobically fermenting, and this digester is on average produced 200 tons of 1500 cubic metres of biogas, 3500 tons of monthly output natural pond liquid and natural pond slags daily.The biogas that biogas that digester produces and UASB reactor produce enters thionizer in the lump and collect gas holder after desulfurization, use the biogas-diesel dual-fuel generating set generating of repacking into by oil electric engine, power is 200kW, and electricity is used for the processing of organic sewage waste residue, little algae cultivation and processing, biological diesel oil refining.The Low Temperature Steam that tail gas produced of generator and hot water are used for the insulation of little algae cultivation and processing, biological diesel oil refining, digester and UASB reactor, and cooled tail gas feeds large-scale gas push type photobioreactor, as the main carbon source of little algae cultivation.Organic sewage and natural pond liquid are after the UASB reactor for treatment, join again and carry out the aerobic biochemical processing in the BAF, further reduce BOD, the COD of organic sewage and natural pond liquid, and ammonia nitrogen is converted into ammonium salt, nitrate or the nitrite that is absorbed by little algae easily, eliminate the peculiar smell of organic sewage and natural pond liquid simultaneously.Organic sewage and natural pond liquid after aerobic biochemical is handled enter in the disinfecting tank after filtering, adding ozone carries out disinfection, kill wherein virus, bacterium, fungi, protozoon and assorted algae, place to join after 1 hour in the nutrient solution blend tank and cultivate main nitrogenous source and phosphorus source as little algae.
Little algae is cultivated and the key equipment of biological diesel oil refining adopt the applicant applied for patent of invention gas push type photobioreactor (gas push type photobioreactor. Chinese invention patent, application number: 200810039168.8; A kind of little algae industrialization production equipment and produce the method for little algae. Chinese invention patent, application number: 200810038075.3), biological diesel oil refining equipment (multifunctional reaction still of production biofuel and working method thereof. Chinese invention patent, application number: 200810039167.3), wherein, the making method of small-sized gas push type photobioreactor be applicant first to file " gas push type photobioreactor. Chinese invention patent; application number: 200810039168.8 ", the making method of large-scale gas push type photobioreactor be applicant first to file " a kind of little algae industrialization production equipment and produce the method for little algae. Chinese invention patent; application number: 200810038075.3 ", the making method of multifunctional reaction still be applicant first to file " multifunctional reaction still of production biofuel and working method thereof. Chinese invention patent, application number: 200810039167.3 ".
At first from algae kind storehouse, take out pavlova viridis algae kind, successively in Erlenmeyer flask, airlift photobioreactor, small-sized gas push type photobioreactor, carry out three grades of expanding species and cultivate, make industrial production algae kind as industrial production device.Industrial production device is to place the outdoor large-scale gas push type photobioreactor that is arranged in parallel by row and row; The width of each reactor is 3 meters, and length is 60 meters, and the degree of depth is 40 centimetres; The water surface total area that pavlova viridis is cultivated is 600 mu.Add nutrient solution during production earlier and make liquid level reach 10 centimetres in large-scale gas push type photobioreactor, the main body of starting breather generation nutrient solution then flows, and inoculates above-mentioned industrial production algae kind subsequently, progressively adds nutrient solution then and makes liquid level reach 20 centimetres.Feed the generator tail gas that is rich in carbonic acid gas by day continuously, carbon dioxide content air after filtration is diluted to 3%, to guarantee the growth of little algae, suitably feeds the breathing that filtrated air is kept little algae at night.With means such as logical hot/cold wind, the ventilation that puts in a skylight, shading temperature adjustment, the insulations of steam/heat water, make the temperature of nutrient solution remain on 15～35 ℃ of suitable micro algae growth.Behind minimizing of the nutrient in the nutrient solution or moisture evaporation, carry out fluid infusion by liquid supplementation pipe, the highest liquid level after the fluid infusion is 30 centimetres.Look micro algae culturing liquid concentration little algae of irregularly gathering, promptly open the liquid discharge pipe valve and discharge algae liquid, when reducing to 15～20 centimetres, the reactor liquid level stops discharge opeing, to control each recovery ratio 10%～30%, at little frond long-pending little, with the more approaching characteristic of density of water, employing feeds the aerating collecting method of generator tail gas and carries out gathering of little algae in air flotation tank, realize the carbonic acid gas of complement lysis in micro algae culturing liquid simultaneously.The nutrient solution that is added in the large-scale gas push type photobioreactor is by the organic sewage and the natural pond liquid that purify after sterilizing, concentration by 3 gram/cubic meters is added ironic citrate, concentration by 0.1 gram/cubic meter is added VITMAIN B1, sneak into the sewage and the 50% raw glycerine by product that produce in the process of rare algae liquid that air flotation tank comes out, little algae oil refining biofuel again, in the nutrient solution blend tank, mix and form.
The pavlova viridis (slurry) that aerating collecting obtains adopts horizontal spiral centrifuge to carry out liquid-solid separation behind the high pressure homogenizer broken wall, and isolated little algae-residue is used to produce little algae composite fertilizer.Isolated liquid phase is added to and is separated into oil phase and water in the ceramic membrane water-and-oil separator, and oil phase is little algae oil.The water material is added in the vacuum concentration still, and thickening temperature is 65 ℃, and concentration time is 1.5 hours.Material after concentrating enters the still of saltouing, and according to the volume of material, the saturation computation ammonium sulfate consumption by 40% slowly is added to solid ammonium sulfate in the still of saltouing, and fully stirs, and precipitates little algae albumen, and the time of saltouing was made as 3 hours.Material after saltouing carries out liquid-solid separation with the high speed centrifugation filter, and isolated solid phase is added to carries out drying and make little algae albumen in the lyophilizer.Isolated liquid phase is added in the alcohol precipitation still, extract little polysaccharides with ethanol precipitation, promptly slowly add concentration and be 80% industrial alcohol under whipped state and carry out alcohol precipitation, the volume ratio of industrial alcohol add-on and original solution was made as 3: 1, and the alcohol precipitation time of repose was made as 9 hours.Material behind the alcohol precipitation carries out liquid-solid separation with the high speed centrifugation filter, and isolated liquid phase is added to carries out rectifying in the ethanol recovery tower, and overhead product is the ethanol of 80% concentration, and bottom product is little algae liquid fertilizer; Isolated solid phase then is added to carries out drying and makes little polysaccharides in the lyophilizer.
Here be the base-catalyzed transesterification method with little algae oil production method of bio-diesel oil,, must remove in advance because little algae oil contains moisture content and free fatty acids.With 4 cubic metres multifunctional reaction still production biofuel of 2 parallel connections, handle 2 batches of little algae oil every day, every batch adds 5 tons of little algae oil.The pre-treatment of little algae oil is to carry out vacuum hydro-extraction earlier, adds the methyl alcohol and the vitriol oil then and carries out pre-esterification reactor, makes the free fatty acids in the stock oil turn to fatty acid methyl ester.After pre-esterification reactor finishes,, calculate the amount of the required sodium hydroxide that just in time neutralizes fully, in reactor, add the sodium hydroxide saturated solution for preparing and carry out neutralization reaction according to added vitriol oil amount.After reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize dehydration, separating methanol, methyl alcohol by rectifying and water sepn after reuse.After the pre-treatment of little algae oil finishes, in reactor, add methyl alcohol and alkaline catalysts sodium hydroxide, carry out transesterification reaction, make the glycerin fatty acid ester reaction in the stock oil generate fatty acid methyl ester.After transesterification reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize separating methanol, direct reuse after methyl alcohol is condensed.Behind the vacuum separating methanol, discharge the mixture of product fatty acid methyl ester and by-product glycerin from reactor, mixture enters in the skimmer settlement separate.Because glycerine, methyl esters proportion differ bigger, two-layer about being divided into very soon in skimmer, glycerine is than the great lower floor that occupies, and methyl esters occupies the upper strata.Raw glycerine after the separation is emitted by the bottom, and wherein one of 50% carbon source of cultivating as little algae is added in the micro algae culturing liquid blend tank, and remaining raw glycerine is delivered to the glycerine workshop and handled.The coarse biodiesel on skimmer top obtains the purified biofuel again after the distillation tower distillation after the water washing tank washing, a whole set of " pollution treatment-foster algae-oil refining " production equipment is produced 3000 tons of biofuel per year.
The density (20 ℃) of little algae biofuel that the present invention produces is 0.868kg/m
3, kinematic viscosity (40 ℃) is 3.8mm
2/ s, water-content (massfraction) are 0.02%, acid number is 0.58mgKOH/g, and calorific value is up to 42MJ/kg, meet China's " diesel-fuel blending with biofuel (BD100) " national standard.
Claims (9)
1. the production method of an organic sewage waste residue treatment, microalgae culturing and oil refining, comprise equalizing tank, anaerobic biochemical reactor, the aerobic biochemical reactor, disinfection tank, the stack retting pond, digester, thionizer, gas holder, the power generation and heat supply device, the nutrient solution blend tank, Erlenmeyer flask, airlift photobioreactor, small-sized gas push type photobioreactor, large-scale gas push type photobioreactor, air flotation tank, high pressure homogenizer, horizontal spiral centrifuge, water-and-oil separator, the vacuum concentration still, the still of saltouing, the high speed centrifugation filter, moisture eliminator, the alcohol precipitation still, the ethanol recovery tower, multifunctional reaction still, skimmer, methanol distillation column, the methyl alcohol basin, water washing tank, distillation tower, biofuel basin equipment is characterized in that may further comprise the steps:
A. the processing of organic sewage waste residue
Organic sewage enters equalizing tank after grid is removed mechanical impurity, regulate the sewage water yield, water quality, pH value, enters then to carry out the anaerobic biological processing in the anaerobic biochemical reactor; The mud that organic waste residues produces with anaerobic biochemical reactor joins the stack retting pond and carries out pile fermentation, and the material behind stack retting joins and carries out anaerobically fermenting in the digester, and the mud that aerobic biochemical reactor is produced joins in the digester in the lump simultaneously; During anaerobically fermenting, the carbon-nitrogen ratio of raw material is (20～30): 1, and solid content is 5%～45% (weight ratio), and the fermentation back produces biogas, natural pond slag and natural pond liquid, and the natural pond slag is as fertilizer, and natural pond liquid joins anaerobic biochemical reactor and carries out the anaerobic biological processing again; The biogas that biogas that digester produces and anaerobic biochemical reactor produce enters thionizer in the lump and collect gas holder after desulfurization, is used for power generation and heat supply; Organic sewage and natural pond liquid are after anaerobic biochemical reactor is handled, join again and carry out the aerobic biochemical processing in the aerobic biochemical reactor, reduce BOD, the COD of organic sewage and natural pond liquid, and ammonia nitrogen is converted into ammonium salt, nitrate or the nitrite that is absorbed by little algae easily, eliminate the peculiar smell of organic sewage and natural pond liquid simultaneously; Organic sewage and natural pond liquid after aerobic biochemical is handled enter in the disinfection tank after filtering, add sterilizing agent and carry out disinfection, and add in the neutralizing agent then and thimerosal, join at last in the nutrient solution blend tank and cultivate main nitrogenous source and phosphorus source as little algae;
B. marsh gas power generation heat supply
The used fuel of power generation and heat supply device is mainly biogas and coarse biodiesel; Power generation and heat supply device electricity is used for the processing of organic sewage waste residue, little algae cultivation and processing, biological diesel oil refining, power generation assembly itself and office household electricity, Low Temperature Steam that is produced and hot water are used for little algae cultivation and processing, biological diesel oil refining, digester and anaerobic biochemical reactor insulation and office life with hot, and insufficient thermoelectricity is by mains supply, heating network heat supply; The stack gas that is rich in carbonic acid gas that the power generation and heat supply device produces feeds large-scale gas push type photobioreactor after purifying, as the main carbon source that little algae is cultivated, insufficient carbon source is by liquid carbon dioxide that adds or sodium bicarbonate supply;
C. utilize carbonic acid gas stack gas, organic sewage and the cultivation of natural pond liquid and gather little algae
At first the algae kind is successively carried out three grades of expanding species in Erlenmeyer flask, airlift photobioreactor, small-sized gas push type photobioreactor and cultivate, make industrial production algae kind as industrial production device; Industrial production device is to place the outdoor large-scale gas push type photobioreactor that is arranged in parallel by row and row, adding nutrient solution earlier in reactor makes liquid level reach 10 centimetres, the main body of starting breather generation nutrient solution then flows, inoculate above-mentioned industrial production algae kind subsequently, and progressively add nutrient solution and make liquid level reach 20 centimetres, feed continuously by day carbon dioxide content after filtration air be diluted to 1%～5% carbonic acid gas stack gas, to guarantee the growth of little algae, feed filtrated air at night and keep the breathing of little algae, adopt logical hot/cold wind, ventilation puts in a skylight, the shading temperature adjustment, steam/heat water insulation is controlled at 15～35 ℃ with the temperature of nutrient solution; After detecting the nutrient minimizing or the decline of algae liquid liquid level in the nutrient solution, carry out fluid infusion by liquid supplementation pipe, the highest liquid level after the fluid infusion is 30 centimetres; Look micro algae culturing liquid concentration little algae of irregularly gathering, promptly open the liquid discharge pipe valve and discharge algae liquid, when the liquid level of large-scale gas push type photobioreactor is reduced to 15～20 centimetres, stop discharge opeing, to control each recovery ratio 10%～30%; Gathering of little algae adopts the aerating collecting method that feeds carbonic acid gas stack gas in air flotation tank to carry out, and realizes the carbonic acid gas of complement lysis in micro algae culturing liquid simultaneously;
D. the full use of oil-containing micro-algae
Little algae that aerating collecting obtains adopts horizontal spiral centrifuge to carry out liquid-solid separation behind the high pressure homogenizer broken wall, and isolated little algae-residue is used to produce little algae composite fertilizer; Isolated liquid phase is added to and is separated into oil phase and water in the water-and-oil separator, and oil phase is little algae oil; The water material is added in the vacuum concentration still, thickening temperature is made as 60～70 ℃, concentration time was made as 1～2 hour, material after concentrating enters the still of saltouing, according to the volume of material, and the saturation computation ammonium sulfate consumption by 30%～50%, solid ammonium sulfate slowly is added in the still of saltouing, fully stir, precipitate little algae albumen, the time of saltouing was made as 2～5 hours; Material after saltouing carries out liquid-solid separation with the high speed centrifugation filter, isolated solid phase is added to carries out drying and makes little algae albumen in the moisture eliminator, isolated liquid phase is added in the alcohol precipitation still, extract little polysaccharides with ethanol precipitation, promptly under whipped state, slowly add concentration and be 70%～95% industrial alcohol and carry out alcohol precipitation, the volume ratio of industrial alcohol add-on and original solution is made as 2～4: 1, and the alcohol precipitation time of repose was made as 3～12 hours; Material behind the alcohol precipitation carries out liquid-solid separation with the high speed centrifugation filter, and isolated liquid phase is added to carries out rectifying in the ethanol recovery tower, and overhead product is the ethanol of 70%～95% concentration, and bottom product is little algae liquid fertilizer, as the foliar nutrient of plant; Isolated solid phase then is added to carries out drying and makes little polysaccharides in the moisture eliminator;
The pre-treatment of e. little algae oil and transesterification reaction
The equipment of the pre-treatment of little algae oil and refining biofuel thereof adopts multifunctional reaction still, in multifunctional reaction still, add algae oil in a subtle way, carry out vacuum hydro-extraction earlier, add the methyl alcohol and the vitriol oil then and carry out pre-esterification reactor, make the free fatty acids in the stock oil turn to fatty acid methyl ester, after pre-esterification reactor finishes, according to added vitriol oil amount, calculate the amount of the required sodium hydroxide that just in time neutralizes fully, in reactor, add the sodium hydroxide saturated solution for preparing and carry out neutralization reaction, after reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize dehydration, separating methanol, methyl alcohol by rectifying and water sepn after reuse; After the pre-treatment of little algae oil finishes, in multifunctional reaction still, add methyl alcohol and alkaline catalysts sodium hydroxide, carry out transesterification reaction, make the glycerin fatty acid ester reaction in the stock oil generate fatty acid methyl ester, after transesterification reaction finishes, under the situation that kettle is continued thermostatically heating, vacuumize separating methanol, direct reuse after methyl alcohol is condensed; Behind the vacuum separating methanol, from multifunctional reaction still, discharge the mixture of product fatty acid methyl ester and by-product glycerin,, crude fatty acid methyl ester is washed and distilled, make biofuel then by after skimmer standing demix or the centrifugation; One of carbon source that in the isolated raw glycerine 10%～70% cultivated as little algae is added in the micro algae culturing liquid blend tank, and remaining raw glycerine is further refining; To the sodium hydroxide sewage that produces in the coarse biodiesel water washing process absorption agent, absorb the nutritive salt that sodium bicarbonate that the back produces is cultivated as little algae as carbonic acid gas; Sodium hydroxide sewage is added in the air flotation tank, heightens the pH value of algae liquid, helps flocculation and the air supporting of little algae; Sodium hydroxide sewage is added in the nutrient solution blend tank, regulates the pH value of nutrient solution; The waste salt that in the vitriol oil and the sodium hydroxide and back generates is added in the nutrient solution blend tank, becomes salinity source and nutritive salt that the little algae of salt water is cultivated.
2.1, ( UASB ) ( IC ) ( EGSB ) ( EC ) ( USR ) ( ABR ) - ( UBF ) ( AF ) ( AHR ) ( ASBR ) ( AEBR ) ( AFBR ) ( ARBC ) ( UFB Biobed ) ( AF+UASB ) 。
3. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described aerobic biochemical reactor is active sludge aeration tank or BAF or aerobic biofilter or biological contact oxidation pond or oxidation ditch or oxidation pond or CASS aerobic biochemical pond or sbr reactor pond or aerobic biological fluid-bed or droplet filter bed or aerobe rotating disk.
4. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described sterilizing agent is ozone or dioxide peroxide or ultraviolet ray.
5. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described neutralizing agent adopts Sulfothiorine.
6. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described power generation and heat supply device is array mode or the array mode of biogas-diesel motor generating set and waste heat boiler or the array mode of gas-turbine generator set and waste heat boiler and steam turbine generating set of gas fuel boiler and steam turbine generating set.
7. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described little algae employing freshwater microalgae or little algae of salty lake water or the little algae of seawater, and classification is chrysophyceae or green alga or diatom or blue-green algae or red algae.
8. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described little algae employing contains the high salt algae of fat or chlorella or Isochrysis galbana 3011 or pavlova viridis.
9. the production method of a kind of organic sewage waste residue treatment, microalgae culturing and oil refining according to claim 1 is characterized in that described moisture eliminator is lyophilizer or spray-dryer.
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