CN100588444C - Treatment method for discharge liquid of ethanol preparation by cassava fermentation - Google Patents

Treatment method for discharge liquid of ethanol preparation by cassava fermentation Download PDF

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CN100588444C
CN100588444C CN200810222825A CN200810222825A CN100588444C CN 100588444 C CN100588444 C CN 100588444C CN 200810222825 A CN200810222825 A CN 200810222825A CN 200810222825 A CN200810222825 A CN 200810222825A CN 100588444 C CN100588444 C CN 100588444C
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liquid
water soluble
solid
soluble algae
waste liquid
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CN101423303A (en
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杜金宝
黄加军
邓立康
邵玉彬
于天杨
罗虎
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Cofco Corp
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Cofco Corp
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Priority to PCT/CN2009/073361 priority patent/WO2010031292A1/en
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/24—Treatment of water, waste water, or sewage by flotation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • 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

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)

Abstract

The invention provides a method for treating waste liquid from a process for making alcohol from cassava by fermentation. The method comprises the following steps: the liquid from a process for makingalcohol from cassava by fermentation is subjected to solid-liquid separation to obtain solid products and liquid products; and then the obtained liquid products are subjected into wastewater treatment, wherein before solid-liquid separation of the waste liquid, water-soluble alginic ester and/or water-soluble alginate are/is added into the waste liquid. The method dramatically reduces time for solid-liquid separation and increases the amount of waste liquid treated in unit time without additional new equipment, thereby overcoming a bottleneck responsible for lower service load of a device used for making alcohol from cassava by fermentation and improving the production capacity of the device used for making alcohol from cassava by fermentation.

Description

A kind of processing method of waste liquid of preparation of ethanol by fermentation of cassava
Technical field
The invention relates to a kind of processing method of waste liquid of preparation of ethanol by fermentation of cassava.
Background technology
Cassava is one of the world three big tuber crops, is the preferred raw materials of producing bio-ethanol.By 2005, China's cassava cultivated area reached 6,570,000 mu, existing tapioca in the whole nation and more than 200 families of alcohol processing factory, and year 500000 tons of starch of production, cassava prepare 250,000 tons of ethanol.Because the waste liquid of preparation of ethanol by fermentation of cassava contains the organic matter of high concentration, the waste liquid of the preparation of ethanol by fermentation of cassava of present most ethanol factory discharging is through effectively handling directly outwards discharging, the water environment in local and downstream caused have a strong impact on.
At present, the processing method of the waste liquid of preparation of ethanol by fermentation of cassava has: 1, burning method, and soon the waste liquid of preparation of ethanol by fermentation of cassava burns after concentrating, and the shortcoming of this method causes secondary pollution easily after burning; 2, with the waste liquid ferment preparation of sludge gas of preparation of ethanol by fermentation of cassava, the shortcoming of this method is that investment is big and the control technology requirement is high.
Therefore, the common at present waste liquid with preparation of ethanol by fermentation of cassava filters and carries out Separation of Solid and Liquid, and the solid residue that Separation of Solid and Liquid is obtained is as feed afterwards, and the waste water that Separation of Solid and Liquid is obtained carries out wastewater treatment.This method is a kind of small investment, the processing method of operation and the waste liquid of environment amenable preparation of ethanol by fermentation of cassava easily.In this case, the disposal ability of Separation of Solid and Liquid just becomes the key factor of decision liquid waste processing ability size.
The problem that the present method that the waste liquid of preparation of ethanol by fermentation of cassava is handled exists is, the excessive cycle of Separation of Solid and Liquid, cause the treating capacity of waste liquid little, and cause the operating load of device of preparation of ethanol by fermentation of cassava lower, production capacity can not reach requirement.
Summary of the invention
The objective of the invention is shortcoming, the processing method of a kind of cycle of Separation of Solid and Liquid than the waste liquid of short preparation of ethanol by fermentation of cassava is provided for the excessive cycle that overcomes the existing Separation of Solid and Liquid that the method for recovery solid residue exists from the waste liquid of preparation of ethanol by fermentation of cassava.
The invention provides a kind of processing method of waste liquid of preparation of ethanol by fermentation of cassava, this method comprises that the waste liquid with preparation of ethanol by fermentation of cassava carries out Separation of Solid and Liquid, obtain solid product and product liquid, afterwards the product liquid that obtains is carried out wastewater treatment, wherein, before being carried out Separation of Solid and Liquid, waste liquid in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
Among the present invention, by in the waste liquid of preparation of ethanol by fermentation of cassava, adding water soluble algae acid esters and/or water soluble algae hydrochlorate, shortened solid-liquid separation time significantly, need not to increase the treating capacity that has improved liquid waste in unit time under the situation of new equipment significantly, thereby the bottleneck that the operating load that has solved the device that causes preparation of ethanol by fermentation of cassava is lower has improved the production capacity of the device of preparation of ethanol by fermentation of cassava.
The specific embodiment
The invention provides a kind of processing method of waste liquid of preparation of ethanol by fermentation of cassava, this method comprises that the waste liquid with preparation of ethanol by fermentation of cassava carries out Separation of Solid and Liquid, obtain solid product and product liquid, afterwards the product liquid that obtains is carried out wastewater treatment, wherein, before being carried out Separation of Solid and Liquid, waste liquid in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
According to the present invention, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate can in very large range change, as long as can shorten solid-liquid separation time, under the preferable case, with respect to the waste liquid of 1000 weight portions, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.05-1 weight portion; More preferably, with respect to the waste liquid of 1000 weight portions, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.1-0.5 weight portion.
The kind of described water soluble algae hydrochlorate can in very large range change, as long as can make collision of molecules aggravation in the waste liquid, making the little molecule that is difficult for precipitation be combined into the bigger flocculate of big molecule formation gets final product, under the preferable case, the relative molecular weight of described water soluble algae hydrochlorate is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell 121/12 ratio of C atomic mass.For example, described water soluble algae hydrochlorate can be selected from one or more in sodium alginate, potassium alginate and the ammonium alginate.The water soluble algae hydrochlorate that meets above-mentioned requirements can be commercially available, for example, the ammonium alginate of the medicinal varek combinations of potassium alginate and ocean, the Handan City Co., Ltd production of the sodium alginate of Nan Yang, Qingdao seaweed industry Co., Ltd production, Qingdao Mingyue Marine Alga Group Corp., Ltd.'s production.
The kind of described water soluble algae acid esters can in very large range change, as long as can make collision of molecules aggravation in the waste liquid, making the little molecule that is difficult for precipitation be combined into the bigger flocculate of big molecule formation gets final product, under the preferable case, the relative molecular weight of described water soluble algae acid esters is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell 121/12 ratio of C atomic mass.For example, described water soluble algae acid esters can be selected from one or more in propylene glycol alginate, ethylene glycol alginate and the alginic acid butanediol ester, is preferably propylene glycol alginate.The water soluble algae acid esters that meets above-mentioned requirements can obtain by well known to a person skilled in the art that method is synthetic, also can be commercially available, for example, the propylene glycol alginate that Qingdao Mingyue Marine Alga Group Corp., Ltd. produces.
Under the preferable case, before being carried out Separation of Solid and Liquid, waste liquid in waste liquid, adds water soluble algae acid esters and water soluble algae hydrochlorate, when adding water soluble algae acid esters and water soluble algae hydrochlorate at the same time, can further shorten solid-liquid separation time, thereby further improve the treating capacity of liquid waste in unit time.In this case, the consumption of water soluble algae acid esters and water soluble algae hydrochlorate can in very large range change, and under the preferable case, with respect to the water soluble algae acid esters of 100 weight portions, the addition of described water soluble algae hydrochlorate is the 10-1000 weight portion.More preferably, with respect to the water soluble algae acid esters of 100 weight portions, the addition of described water soluble algae hydrochlorate is the 40-300 weight portion.
According to the present invention, described Separation of Solid and Liquid can be the various solid-liquid separating methods of routine, as filtering, for example, can filter by filter press, for example, the chamber-type press filter that Jingjin Filter Press Group Co.,Ltd produces.The condition of described filtration can in very large range change, and under the preferable case, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and filter time is 1-3 hour.
But, the present inventor finds, when using common chamber-type press filter that the waste liquid of preparation of ethanol by fermentation of cassava is filtered, waste liquid enters between the chamber filter plate of filter press, solid particle is trapped in the space between the filter plate by the filter medium of filter plate, liquid then passes through filter medium, discharge outside the filter press by portalling, continuity along with filter process, the thickness of solid product increases gradually, the resistance of dehydration increases exponentially thereupon, thereby causes the rapid decline for the treatment of capacity, and because the restriction of the character of chamber filter plate own, filter pressure can't further improve (generally below 1MPa), thereby can't further improve the solid content that obtains solid product, thereby cause the chemical oxygen demand value of the product liquid after the Separation of Solid and Liquid higher, increase the pressure of subsequent wastewater treatment.
Therefore, under the preferable case, described Separation of Solid and Liquid is by filtering and squeeze realization to described waste liquid.The present invention filters and squeezes by the waste liquid to preparation of ethanol by fermentation of cassava, has reduced the COD value of the product liquid that obtains after the Separation of Solid and Liquid significantly, has reduced the pressure of subsequent wastewater treatment; Under the preferable case, described filtration and squeezing can realize by using diaphragm filter press, diaphragm filter press promptly has the filtering function identical with the common diaphragm filter press, have again solid product is squeezed and function that it is dewatered once more, in diaphragm filter press, common filter plate and membrane filter plate are spaced, the middle central layer of described membrane filter plate and both sides barrier film compress and form two Sealed sandwiches, the filtering function of described membrane filter plate is identical with common filter plate, but increased pressing function, promptly, the elastic reaction of barrier film after filtering end, extrusion medium is injected into the sealant from middle central layer hand-hole, owing to can carry out the blow-up squeezing to the solid product after filtering, improve the solid content of solid product, thereby reduced the COD value of the product liquid that obtains after the Separation of Solid and Liquid.
The common chamber filter plate and the quantity of membrane filter plate can be adjusted according to the concentration of waste liquid in the described diaphragm filter press, under the preferable case, the quantity of common chamber filter plate is 50-60, described common chamber filter plate can be commercially available, for example the chamber filter plate of Jingjin Filter Press Group Co.,Ltd's production; The quantity of membrane filter plate is 50-60, and described membrane filter plate can be commercially available, for example 1250 type membrane filter plates of Jingjin Filter Press Group Co.,Ltd's production; Common chamber filter plate is spaced with membrane filter plate and the ratio of the quantity of different chamber filter plate and the quantity of membrane filter plate is 1: 1; The diaphragm filter press that meets above-mentioned requirements can be commercially available, for example, and the X that Jingjin Filter Press Group Co.,Ltd produces M AZG600/1500 * 2000U B KThe diaphragm filter press of model.
The inventor finds, uses diaphragm filter press not only can reduce the COD value of the product liquid that obtains after the Separation of Solid and Liquid significantly, can also significantly reduce the content that squeezes impurity in the water of removing, and has reduced the wearing and tearing of impurity to equipment, has reduced maintenance cost.
Among the present invention, the waste liquid of described preparation of ethanol by fermentation of cassava is meant by cassava and ferments when preparing ethanol, distills out after the ethanol that obtains residual solidliquid mixture.
Among the present invention, the condition of described filtration and squeezing can in very large range change, and under the preferable case, it is the 30000-35000 mg/litre that the condition of described filtration and squeezing makes the chemical oxygen demand value of the product liquid that obtains; More preferably, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and filter time is 1-2 hour; The condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
Among the present invention, described squeeze pressure can realize that described extrusion medium can be diaphragm filter press various extrusion medium commonly used by charge into extrusion medium in diaphragm filter press, and for example, described extrusion medium can be compressed air and/or water.
According to the present invention, the method for described wastewater treatment is had no particular limits, for example, can carry out wastewater treatment by disclosed method among the CN1202032C.For example, the product liquid that Separation of Solid and Liquid is obtained feeds anaerobic reactor and aerobic reactor, leaves standstill, with the supernatant oxidation and remove suspension in the supernatant.
Among the present invention, described anaerobic reactor is conventionally known to one of skill in the art, in the described anaerobic reactor anaerobic grain sludge is housed, contain anaerobe in the described anaerobic grain sludge, the kind of this anaerobe is conventionally known to one of skill in the art, for example, Bacteroides succinogenes (Bacteriodessuccinogenes), Butyrivibrio fibrisolvens (Butyribibrio fibrisolve), ruminococcus flavefaciens (Ruminococcus flavfaciens), Ruminococcus albus (Ruminococcus albus) etc.; When product liquid passed through anaerobic reactor, the organic matter in the product liquid was degraded; The kind of described anaerobic grain sludge is conventionally known to one of skill in the art, can be commercially available, for example the anaerobic grain sludge of Paques Environmental Technology's production.
The time of staying of described product liquid in anaerobic reactor can be selected according to the kind of product liquid, and under the preferable case, the time of stop is 25-35 hour.
Reaction condition in the described anaerobic reactor can in very large range change, and for example, the reaction condition in the described anaerobic reactor comprises that volumetric loading is 20-25kgCOD/m 3.d, temperature is 30-40 ℃, and the pH value is 6.5-7.5.
Described aerobic reactor is conventionally known to one of skill in the art, under the preferable case, product liquid can be fed A/O reactor (anoxic/Aerobic Pond) and carry out Aerobic Process for Treatment, in the described A/O reactor aerobic particle mud is housed, when product liquid is flowed through, organic matter in the aerobic flora decomposition water, be converted into the idiotrophic material, the kind of described aerobic particle mud is conventionally known to one of skill in the art, can be commercially available, for example the aerobic particle mud of the green source of Beijing Feng Ze Environmental Technology AS production.The time of staying of described product liquid in aerobic reactor can be selected according to the kind of product liquid, and under the preferable case, the time of stop is 40-60 hour.
Reaction condition in the described aerobic reactor can in very large range change, and under the preferable case, the reaction condition in the described aerobic reactor comprises that volumetric loading is 0.1-0.2kgBOD/m 3.d, temperature is 20-40 ℃, and the pH value is 7-8, and dissolved oxygen is 1-3mg/l, and described dissolved oxygen is meant when product liquid is carried out aeration, the content of oxygen in water.
According to the present invention, will leave standstill by the waste water of anaerobic reactor and aerobic reactor, with the supernatant oxidation and remove suspension in the supernatant.
Described method with the supernatant oxidation is conventionally known to one of skill in the art, for example use oxidant that supernatant is carried out oxidation, the kind of described oxidant is conventionally known to one of skill in the art, for example can be in clorox, calcium hypochlorite, ferric trichloride and the Na2Fe04 one or more, the time of described oxidation processes is 0.5-1.5 hour.
According to the present invention, can the suspended substance removal in the supernatant be fallen by various known methods, for example, supernatant can be fed flotation tank and carry out the air supporting processing, the flocculant that described flotation tank adopts is conventionally known to one of skill in the art, for example can be the aluminium based flocculating agent, in iron-based flocculating agent and the composite flocculation agent one or more, above-mentioned flocculant can be commercially available, for example, the bodied ferric sulfate (PFS) that Huizhou 3R Environmental Chemical Co., Ltd. produces, poly-ferric chloride (PFC), polymeric biacid iron aluminium (PFSIC) and polymerized ferric-aluminum chloride (PFAS), the surfaceloadingrate of described flotation tank is 36-72m 3/ m 2.h, the time of staying of described supernatant in flotation tank is 3-5 minute.
To do further specific descriptions to the present invention by specific embodiment below.
Embodiment 1
In water content is to add propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd. of 10 kilograms in the waste liquid (100 tons) of the preparation of ethanol by fermentation of cassava of 95 weight %, relative molecular weight is 40000), afterwards waste liquid is joined in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd), after being filled, filters by filter press, in the described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, filter time is 2 hours, obtain the solid product that water content is 75 weight %, and the product liquid A1 after the Separation of Solid and Liquid, the liquid waste processing amount (separate unit) in time that Separation of Solid and Liquid is required and unit interval is as shown in table 1.
Comparative Examples 1
Filter according to the waste liquid of the method identical preparation of ethanol by fermentation of cassava with embodiment 1, different is not add propylene glycol alginate, obtain the solid product that water content is 75 weight %, and the product liquid CA1 after the Separation of Solid and Liquid, the liquid waste processing amount (separate unit) in time that Separation of Solid and Liquid is required and unit interval is as shown in table 1.
Embodiment 2
In water content is to add 30 kilograms sodium alginate (Nan Yang, Qingdao seaweed industry Co., Ltd in the waste liquid (100 tons) of the preparation of ethanol by fermentation of cassava of 95 weight %, relative molecular weight is 80000), afterwards waste liquid is joined in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd), after being filled, filters by filter press, in the described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, filter time is 1.8 hours, obtain the solid product that water content is 75 weight %, and the product liquid A2 after the Separation of Solid and Liquid, the liquid waste processing amount (separate unit) in time that Separation of Solid and Liquid is required and unit interval is as shown in table 1.
Embodiment 3
In water content is to add potassium alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd. of 15 kilograms in the waste liquid (100 tons) of the preparation of ethanol by fermentation of cassava of 95 weight %, relative molecular weight is 150000) and propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd. of 15 kilograms, relative molecular weight is 100000), afterwards waste liquid is joined in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd), in the described chamber-type press filter, after being filled, filters by filter press, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, filter time is 1.4 hours, obtain the solid product that water content is 75 weight %, and the product liquid A3 after the Separation of Solid and Liquid.Liquid waste processing amount (separate unit) in time that Separation of Solid and Liquid is required and unit interval is as shown in table 1.
Table 1
The embodiment numbering The solid product water content Separation of Solid and Liquid is consuming time Treating capacity (ton/hour)
Embodiment 1 75 weight % 2 hours 42
Comparative Examples 1 75 weight % 4.5 hour 18.7
Embodiment 2 75 weight % 1.8 hour 46.7
Embodiment 3 75 weight % 1.4 hour 60
As can be seen from the above table, the processing method of the waste liquid of preparation of ethanol by fermentation of cassava provided by the invention, shortened solid-liquid separation time significantly, need not to increase the treating capacity that has improved liquid waste in unit time under the situation of new equipment significantly, thereby the bottleneck that the operating load that has solved the device that causes preparation of ethanol by fermentation of cassava is lower has improved the production capacity of the device of preparation of ethanol by fermentation of cassava.
Embodiment 4
In water content is to add 10 kilograms ammonium alginate (the medicinal varek combinations in ocean, Handan City Co., Ltd in the waste liquid (100 tons) of the preparation of ethanol by fermentation of cassava of 95 weight %, relative molecular weight is 100000) and propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd. of 10 kilograms, relative molecular weight is 50000), afterwards waste liquid is joined in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd), after being filled, filters by filter press, in the described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, filter time is 1.8 hours, obtains the product liquid A4 after the Separation of Solid and Liquid.
By the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product A 4, the result is as shown in table 1.
A4 stirs with product liquid, forms suspension; Get suspension 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity among the product liquid A4 that obtains obtaining after the Separation of Solid and Liquid, the result is as shown in table 2.
Anaerobic-aerobic Waste Water Treatment by biomass energy Co., Ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the product liquid A4 that obtains, and this Waste Water Treatment mainly comprises pre-acidization, anaerobic reactor, A/O system, sedimentation basin, oxidation reaction pond, flotation tank and the sludge concentration tank in the pre-acidification pool.Described anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, described aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Described oxidation reaction pond adopts clorox to carry out oxidation; Described flotation tank adopts aluminium polychloride (Huizhou 3R Environmental Chemical Co., Ltd.) and anion PAM -(polyacrylamide) decolours to waste water; Described sludge concentration tank plays the effect of thickened sludge.
The time of staying of described product liquid in anaerobic reactor is 25 hours, and the reaction condition in the described anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m 3.d, temperature is 35 ℃, and the pH value is 6.8, and the product liquid that flows out from anaerobic reactor enters the A/O system and carries out Aerobic Process for Treatment, the time of staying of described product liquid in the A/O system is 50 hours, and the reaction condition in the described A/O system comprises that volumetric loading is 0.1kgBOD/m 3.d, temperature is 20 ℃, and the pH value is 7, and dissolved oxygen is 1mg/l; Water after handle the aeration tank enters the sedimentation basin sedimentation, and supernatant enters the oxidation of oxidation reaction pond, and the time of described oxidation is 0.5 hour, enters air-flotation system again and handles the back discharge, and the surfaceloadingrate of described flotation tank is 36m 3/ m 2.h, the time of staying of described supernatant in flotation tank is 3 minutes.
Product liquid D1 after obtaining handling, by the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product D 1, the result is as shown in table 2.
Embodiment 5
Filter according to the waste liquid of the method identical with embodiment 4 to preparation of ethanol by fermentation of cassava, different is that waste liquid is joined diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X M AZG600/1500 * 2000U B K) in carry out Separation of Solid and Liquid, in the described diaphragm filter press, replace 50 common chamber filter plate (Jingjin Filter Press Group Co.,Ltd with 50 membrane filter plates (Jingjin Filter Press Group Co.,Ltd, 1250 types), chamber filter plate), and common chamber filter plate and membrane filter plate be spaced; The condition of described filtration comprises that the pressure of filtration is 0.8MPa, and filter time is 1 hour; Charge into the extrusion medium air afterwards in membrane filter plate, the solid product after filtering is squeezed, the pressure of described squeezing is 10MPa, and the time of squeezing is 0.8 hour, obtains product liquid A5.
By the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product A 5, the result is as shown in table 2.
A5 stirs with product liquid, forms suspension; Get suspension 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity among the product liquid A5 that obtains obtaining after the Separation of Solid and Liquid, the result is as shown in table 2.
Anaerobic-aerobic Waste Water Treatment by biomass energy Co., Ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the product liquid A5 that obtains, and this Waste Water Treatment mainly comprises pre-acidization, anaerobic reactor, A/O system, sedimentation basin, oxidation reaction pond, flotation tank and the sludge concentration tank in the pre-acidification pool.Described anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, described aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Described oxidation reaction pond adopts clorox to carry out oxidation; Described flotation tank adopts aluminium polychloride (Huizhou 3R Environmental Chemical Co., Ltd.) and anion PAM -(polyacrylamide) decolours to waste water; Described sludge concentration tank plays the effect of thickened sludge.
The time of staying of described product liquid in anaerobic reactor is 35 hours, and the reaction condition in the described anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m 3.d, temperature is 38 ℃, and the pH value is 7.2, and the product liquid that flows out from anaerobic reactor enters the A/O system and carries out Aerobic Process for Treatment, the time of staying of described product liquid in the A/O system is 55 hours, and the reaction condition in the described A/O system comprises that volumetric loading is 0.2kgBOD/m 3.d, temperature is 40 ℃, and the pH value is 8, and dissolved oxygen is 3mg/l; Water after handle the aeration tank enters the sedimentation basin sedimentation, and supernatant enters the oxidation of oxidation reaction pond, and the time of described oxidation is 1.5 hours, discharges after air supporting is handled again, and the surfaceloadingrate of described flotation tank is 65m 3/ m 2.h, the time of staying of described supernatant in flotation tank is 5 minutes.Product liquid D2 after obtaining handling, by the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product D 2, the result is as shown in table 2.
Embodiment 6
Filter according to the waste liquid of the method identical with embodiment 5 to preparation of ethanol by fermentation of cassava, difference is: the condition of described filtration comprises that the pressure of filtration is 0.8MPa, and filter time is 1 hour; Charge into the extrusion medium air afterwards in membrane filter plate, the solid product after filtering is squeezed, the pressure of described squeezing is 10MPa, and the time of squeezing is 0.5 hour, obtains product liquid A6.
By the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product A 6, the result is as shown in table 2.
A6 stirs with product liquid, forms suspension; Get suspension 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity among the product liquid A6 that obtains obtaining after the Separation of Solid and Liquid, the result is as shown in table 2.
Anaerobic-aerobic Waste Water Treatment by biomass energy Co., Ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the product liquid A6 that obtains, and this Waste Water Treatment mainly comprises pre-acidization, anaerobic reactor, A/O system, sedimentation basin, oxidation reaction pond, flotation tank and the sludge concentration tank in the pre-acidification pool.Described anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, described aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Described oxidation reaction pond adopts clorox to carry out oxidation; Described flotation tank adopts aluminium polychloride (Huizhou 3R Environmental Chemical Co., Ltd.) and anion PAM -(polyacrylamide) decolours to waste water; Described sludge concentration tank plays the effect of thickened sludge.
The time of staying of described product liquid in anaerobic reactor is 30 hours, and the reaction condition in the described anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m 3.d, temperature is 36 ℃, and the pH value is 7.0, and the product liquid that flows out from anaerobic reactor enters the A/O system and carries out Aerobic Process for Treatment, the time of staying of described product liquid in the A/O system is 45 hours, and the reaction condition in the described A/O system comprises that volumetric loading is 0.12kgBOD/m 3.d, temperature is 30 ℃, and the pH value is 7.5, and dissolved oxygen is 2mg/l; Water after handle the aeration tank enters the sedimentation basin sedimentation, and supernatant enters the oxidation of oxidation reaction pond, and the time of described oxidation is 1 hour, discharges after air supporting is handled again, and the surfaceloadingrate of described flotation tank is 50m 3/ m 2.h, the time of staying of supernatant in flotation tank is 5 minutes.Product liquid D3 after obtaining handling, by the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate method tracer liquid product D 3, the result is as shown in table 2.
Table 2
Figure C20081022282500161
As can be seen from Table 2, the COD value of the product liquid A5 that obtains after embodiment 5 Separation of Solid and Liquid is 34100 mg/litre, be markedly inferior to COD value 50000 mg/litre of the product liquid A4 that obtains after embodiment 4 Separation of Solid and Liquid, after carrying out wastewater treatment under the identical condition, the COD value of the product liquid D2 that embodiment 5 obtains is 87 mg/litre, be markedly inferior to COD value 350 mg/litre that embodiment 4 carries out the product liquid D1 that obtains after the wastewater treatment, explanation filters and squeezes the chemical oxygen demand value that can reduce the product liquid that obtains after the Separation of Solid and Liquid significantly by using diaphragm filter press to waste liquid, thereby reduce the pressure of wastewater treatment significantly, and the waste water after handling can satisfy environment requirement.

Claims (11)

1, a kind of processing method of waste liquid of preparation of ethanol by fermentation of cassava, this method comprises that the waste liquid with preparation of ethanol by fermentation of cassava carries out Separation of Solid and Liquid, obtain solid product and product liquid, the product liquid that obtains is carried out wastewater treatment, it is characterized in that, before waste liquid is carried out Separation of Solid and Liquid, in waste liquid, add water soluble algae acid esters and water soluble algae hydrochlorate; With respect to the water soluble algae acid esters of 100 weight portions, the addition of described water soluble algae hydrochlorate is the 10-1000 weight portion.
2, method according to claim 1, wherein, with respect to the waste liquid of 1000 weight portions, the consumption of described water soluble algae acid esters and water soluble algae hydrochlorate is the 0.05-1 weight portion.
3, method according to claim 2, wherein, with respect to the waste liquid of 1000 weight portions, the consumption of described water soluble algae acid esters and water soluble algae hydrochlorate is the 0.1-0.5 weight portion.
4, method according to claim 1, wherein, with respect to the water soluble algae acid esters of 100 weight portions, the addition of described water soluble algae hydrochlorate is the 40-300 weight portion.
5, according to any described method among the claim 1-4, wherein, the relative molecular weight of described water soluble algae hydrochlorate is 30000-200000, described water soluble algae hydrochlorate is selected from one or more in sodium alginate, potassium alginate and the ammonium alginate, the relative molecular weight of described water soluble algae acid esters is 30000-200000, and described water soluble algae acid esters is a propylene glycol alginate.
6, method according to claim 1, wherein, described Separation of Solid and Liquid is by filtering and squeeze realization to described waste liquid.
7, method according to claim 6, wherein, described filtration and squeezing realize that by diaphragm filter press it is the 30000-35000 mg/litre that the condition of described filtration and squeezing makes the chemical oxygen demand value of the product liquid that obtains.
8, method according to claim 7, wherein, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, filter time is 1-2 hour; The condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
9, method according to claim 1, wherein, described wastewater treatment comprises that waste water that Separation of Solid and Liquid is obtained feeds anaerobic reactor and aerobic reactor, leaves standstill, with the supernatant oxidation and remove suspension in the supernatant.
10, method according to claim 9, wherein, the time of staying of described waste water in anaerobic reactor is 25-35 hour, the reaction condition in the described anaerobic reactor comprises that volumetric loading is 20-25kgCOD/m 3.d, temperature is 30-40 ℃, and the pH value is 6.5-7.5.
11, method according to claim 9, wherein, the time of staying of described waste water in aerobic reactor is 40-60 hour, the reaction condition in the described anaerobic reactor comprises that volumetric loading is 0.1-0.2kgBOD/m 3.d, temperature is 20-40 ℃, and the pH value is 7-8.
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