WO2014005484A1 - 一种提高含蛋白质废水生物产氢的方法 - Google Patents

一种提高含蛋白质废水生物产氢的方法 Download PDF

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WO2014005484A1
WO2014005484A1 PCT/CN2013/077690 CN2013077690W WO2014005484A1 WO 2014005484 A1 WO2014005484 A1 WO 2014005484A1 CN 2013077690 W CN2013077690 W CN 2013077690W WO 2014005484 A1 WO2014005484 A1 WO 2014005484A1
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protein
wastewater
protein wastewater
anaerobic
hydrogen
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French (fr)
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陈银广
肖乃东
王怀臣
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Tongji University
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Tongji University
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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
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • 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
    • C02F3/28—Anaerobic digestion processes
    • 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
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/348—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the way or the form in which the microorganisms are added or dosed
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/30—H2
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/10—Temperature conditions for biological treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/10—Energy recovery
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/06—Nutrients for stimulating the growth of microorganisms
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies

Definitions

  • the invention belongs to the technical field of environmental protection, and particularly relates to a method for improving hydrogen production by protein. Background technique
  • the protein Under anaerobic conditions, the protein is first hydrolyzed into polypeptides and amino acids, which are then converted to short-chain fatty acids during the acidification stage to produce hydrogen, which is ultimately converted to methane during the methanation stage.
  • To obtain intermediate hydrogen it is necessary to inhibit the activity of the methanogen to control the fermentation process in the acidification stage, and it is also necessary to suppress the activity of hydrogen-consuming bacteria other than the methanogen.
  • proteins undergo a slow degradation rate under anaerobic conditions and incomplete degradation, and the hydrolysis process is a limiting step in the anaerobic degradation of proteins.
  • UV-C Ultraviolet light
  • tyrosine, tryptophan and phenylalanine in proteins can destroy the natural structure of proteins and cause protein unfolding. Conducive to the hydrolysis of proteins and subsequent bio-hydrogen production. Summary of the invention
  • the method for improving the biohydrogen production of protein wastewater proposed by the invention has the following specific steps:
  • the protein waste water is added to the ultraviolet pretreatment device, the ultraviolet lamp with the ballast is opened, and the immersion type water irradiation is used to maintain the ultraviolet irradiation intensity of 10 ⁇ 40w/L waste water, the thickness of the water layer is 2 ⁇ 10cm, and the magnetic force is simultaneously opened.
  • the agitator and the circulating cooling water are used to maintain the temperature of the protein wastewater in the ultraviolet irradiation process at 20 to 25 ° C, and ultraviolet irradiation for 0.5 to 10 hours; and the pretreated protein waste water is obtained;
  • the pretreated protein wastewater obtained in the step (1) is added to the anaerobic reactor, and the heat-treated anaerobic activated sludge is inoculated to make the activated sludge concentration (SS) in the anaerobic reactor 3500_4500 mg/L.
  • SS activated sludge concentration
  • Anaerobic fermentation in a shaker for 72 ⁇ 96h the hydrogen volume and hydrogen content in the anaerobic reactor are measured every 12h, and the pH of the solution in the anaerobic reactor is maintained neutral during the whole process; wherein: chloroform
  • the amount of addition is 0.01% ⁇ 0.05% of the volume of protein wastewater, and the amount of trace elements added is 0.33% of the volume of protein wastewater.
  • the ultraviolet irradiation time of the protein wastewater in the step (1) is l ⁇ 3h, and the thickness of the water layer is 2 ⁇ 4cm.
  • the amount of chloroform added in the step (2) is 0.02% to 0.03% of the volume of the protein wastewater.
  • the anaerobic activated sludge after the heat treatment is a sludge which is heated and boiled at 102 ° C for 30 minutes.
  • each 1 L of the trace element solution contains 2.0 g of EDTA-2Na, 2.0 g of FeS0 4 7H 2 0, O.lg of H 3 BO 3 , 0.1 g of CoCl 6H 2 O, 0.1. g ZnCl 2 , 0.05 g Cu (NO 3 ) 5H 2 O, 0.1 g MnCl 4H 2 0, 0.75 g Na 2 Mo0 4 , 0.02 g NiCl 6H 2 0 and O. OOlg Na 2 Se0 3 , Formulated from distilled water, the total volume is lLo
  • step (2) the pH of the mixture is adjusted to be neutral by using NaOH or HCL.
  • a method for improving the biohydrogen production of protein is proposed.
  • the combination of UV denaturation and biohydrogen production of protein increases the protein conversion rate and hydrogen production by 2.79 times and 2.99 times, respectively.
  • Protein ultraviolet irradiation pretreatment is beneficial to protein unfolding, which makes its conformation change, loose structure and increases the point of entry of protease in fermentation stage, which is beneficial to the biological utilization of protein and hydrogen production. Compared with other protein denaturation methods, UV pretreatment has no residual and secondary pollution, and the advantages are obvious.
  • Figure 1 is a UV pretreatment apparatus for protein wastewater of the present invention.
  • 1 is an ultraviolet lamp ballast
  • 2 is circulating cooling water
  • 3 is a protein solution
  • 4 is a quartz tube
  • 5 is a violet lamp
  • 6 is a magnetic stirrer rotor
  • 7 is a magnetic stirrer.
  • the ultraviolet pretreatment device for protein wastewater in the following examples is shown in Figure 1.
  • the ultraviolet irradiance of protein wastewater is immersed in water, and the magnetic stirrer and external circulating cooling water are turned on.
  • the pretreated protein is obtained after UV irradiation for a certain period of time. Waste water.
  • 300mL of protein wastewater with COD of 5000mg/L, NaHC0 3 5g/L, K 2 HP0 3 0.183g/L was not subjected to UV pretreatment, directly added to the anaerobic reactor for blank reference, and inoculated with heat treatment (102 °C) After 30 minutes, the anaerobic activated sludge has a sludge concentration (SS) of 4000 ⁇ 200 mg/L in the reactor, and after adding 1 ml of trace elements and 0.02% (6 ( ⁇ L) volume ratio of chloroform. Adjust the pH of the mixture to 7 ⁇ 0.2 with NaOH or HCL.
  • SS sludge concentration
  • Example 1 The same protein wastewater as in Example 1 was added to the ultraviolet pretreatment apparatus shown in Fig. 1, and the submerged water was used to maintain the ultraviolet irradiation intensity of 14 w/L of wastewater, and the thickness of the water layer was 3 cm; at the same time, the magnetic stirrer was turned on and The cooling water is circulated to maintain the temperature of the protein wastewater in the ultraviolet irradiation process at 20 ⁇ 25 °C, and the pretreated protein wastewater is obtained after ultraviolet irradiation for 0.5-5 hours.
  • Table 1 The properties are shown in Table 1.
  • UV pretreated 2 h of protein wastewater was added to the anaerobic reactor for fermentation to produce hydrogen.
  • Other operations were as in Example 1. After the end of the fermentation, the mixture was centrifuged at 4500 rpm for 15 min to obtain a supernatant, and the total amount of volatile acid in the supernatant was measured. It was 3600.4 mg COD/L; the cumulative hydrogen production after fermentation for 84 h was 78.2 mL/g-COD.
  • the unit of COD and VFAs is mg-COD/L, and the unit of NH 4 + -N is mg/L; the absorbance at 280 nm is the value after the solution is diluted 10 times, and is dimensionless.
  • the protein wastewater was added to the ultraviolet pretreatment device to maintain the ultraviolet irradiation intensity of lOw/L wastewater, the thickness of the water layer was 2 cm, and the ultraviolet irradiation was 0.5 h. Then, 300 mL of the pretreated solution was added to the anaerobic reactor for fermentation to produce hydrogen, and other operations were as in Example 2. After the fermentation, the total amount of volatile acid in the supernatant was 1965.4 mg COD/L ; after 84 h of fermentation, the cumulative hydrogen production was 45.5 mIJg-COD.
  • the protein wastewater was added to the ultraviolet pretreatment apparatus to maintain the ultraviolet irradiation intensity of 40 w/L of wastewater, the thickness of the water layer was 10 cm, and the ultraviolet irradiation was carried out for 0.5 h. Then, 300 mL of the pretreated solution was added to the anaerobic reactor for fermentation to produce hydrogen, and other operations were as in Example 2. After the end of the fermentation, the total amount of volatile acid in the supernatant was 1678.4 mg COD/L; after 72 h of fermentation, the cumulative hydrogen production was 39.2 mL/g-COD.
  • the protein wastewater was added to the ultraviolet pretreatment device to maintain the ultraviolet irradiation intensity of lOw/L wastewater, the thickness of the water layer was 10 cm, and the ultraviolet irradiation was carried out for 10 hours. Then, 300 mL of the pretreated solution was added to the anaerobic reactor for fermentation to produce hydrogen, and other operations were as in Example 2. After the end of the fermentation, the total amount of volatile acid in the supernatant was 2746.3 mg COD/L ; after 84 h of fermentation, the cumulative hydrogen production was 57.2 mIJg-COD.
  • the protein wastewater was added to the ultraviolet pretreatment apparatus to maintain the ultraviolet irradiation intensity of 14 w/L of wastewater, the thickness of the water layer was 3 cm, and ultraviolet irradiation for 2 hours. Then, 300 mL of the pretreated solution was added to the anaerobic reactor for fermentation to produce hydrogen, and 0.01% (30 ⁇ M of chloroform was used to inhibit the homoacetogenic bacteria, and other operations were as in Example 2. The supernatant was measured after the fermentation was completed. The total amount of volatile acid was 3557.9 mg COD/L; the cumulative hydrogen production after fermentation for 84 h was 75.1 mL/g-COD.
  • the protein wastewater was added to the ultraviolet pretreatment apparatus to maintain the ultraviolet irradiation intensity of 14 w/L of wastewater, the thickness of the water layer was 3 cm, and ultraviolet irradiation for 2 hours. Then, 300 mL of the pretreated solution was added to the anaerobic reactor for fermentation to produce hydrogen, and 0.05% (15 CVL) of chloroform was added to inhibit the homoacetogenic bacteria. Other operations were as in Example 2. After the end of the fermentation, the total amount of volatile acid in the supernatant was 3540.3 mg COD/L; after 96 h of fermentation, the cumulative hydrogen production was 77.0 mL/g-COD.

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Description

-种提高含蛋白质废水生物产氢的方法 技术领域
本发明属于环境保护技术领域， 具体涉及一种提高蛋白质生物产氢的方法。 背景技术
当前， 城市污水处理厂每年产生大量的剩余污泥， 同时食品加工行业每年产生大量的生 产废水。 除了碳水化合物和油脂， 蛋白质是剩余污泥和食品加工行业污水的主要有机组分。 蛋白质占剩余污泥固体组分 （SS) 的 40%以上， 而食品加工 （如大豆、 乳清和鱼类） 过程也 产生大量产生含蛋白质的废水。 将高蛋白质含量的剩余污泥和污水无害化、 资源化是环保领 域的一个重要课题。 同时， 氢气作为一种清洁的能源有着广泛的用途， 如果将高蛋白质含量 的废物厌氧发酵生物产氢可以同时实现废物的无害化和资源化， 有着广阔的前景。
在厌氧条件下， 蛋白质首先水解成多肽和氨基酸， 然后在酸化阶段转化成短链脂肪酸并 产生氢气， 酸化产物最终在甲烷化阶段转化成甲烷。 要得到中间产物氢气需要抑制甲烷菌的 活性将发酵过程控制在酸化阶段， 而且还需要抑制除甲烷菌以外其它耗氢菌的活性。 但是， 与碳水化合物不同， 蛋白质在厌氧条件下降解速率很慢而且降解不完全， 水解过程是蛋白质 厌氧降解的限制性步骤。
紫外线特别是 UV-C是一种可以使蛋白质变性的物理方法， 蛋白质中的酪氨酸、 色氨酸 和苯丙氨酸吸收紫外线后可使蛋白质的天然结构受到破坏而发生蛋白质去折叠， 从而有利于 蛋白质的水解和后续的生物产氢。 发明内容
本发明的目的在于提供一种提高蛋白质废水生物产氢的方法。
本发明提出的提高蛋白质废水生物产氢的方法， 具体步骤如下：
( 1 )： 蛋白质废水紫外线照射预处理
将蛋白质废水加入紫外预处理装置中，打开带有镇流器的紫外灯，采用浸没式水内照射， 保持紫外线照射强度为 10~40w/L废水， 水层厚度为 2~10cm， 同时打开磁力搅拌器和循环冷 却水， 使紫外线照射过程中蛋白质废水的温度维持在 20~25°C， 紫外照射 0.5~10h; 得到预处 理后的蛋白质废水；
(2)： 预处理后的蛋白质废水在中性 pH条件下生物产氢
将步骤 (1)得到的预处理后的蛋白质废水加入到厌氧反应器内， 接种加热处理后的厌氧活 性污泥， 使厌氧反应器内的活性污泥浓度 （SS ) 为 3500_4500mg/L， 再加入微量元素和三氯 甲烷后， 调节混合物的 pH为中性， 经氮气吹扫厌氧反应器 2min后用橡胶塞密封使其保持厌 氧状态， 并将厌氧反应器在中温条件下， 在摇床内厌氧发酵 72~96h， 每 12h测定一次厌氧反 应器内的氢气体积和氢气含量， 并在整个过程中维持厌氧反应器内溶液 pH为中性； 其中： 三氯甲烷添加量为蛋白质废水体积的 0.01%~0.05%， 微量元素加入量为蛋白质废水体积的 0.33%。
本发明中， 步骤 （1 ) 中蛋白质废水的紫外照射时间为 l~3h， 水层厚度为 2~4cm。
本发明中， 步骤 （2) 中三氯甲烷添加量为蛋白质废水体积的 0.02%~0.03%。 本发明中， 加热处理后的厌氧活性污泥为 102 °C加热煮沸 30min的污泥。
本发明中，步骤 (2)中每 1L微量元素溶液中含有 2.0g的 EDTA-2Na、 2.0g的 FeS04 7H20、 O. lg的 H3BO3、0.1g的 CoCl 6H2O、0.1g的 ZnCl2、0.05g的 Cu (NO3) 5H2O、0.1g的 MnCl 4H20、 0.75g的 Na2Mo04、 0.02g的 NiCl 6H20和 O.OOlg的 Na2Se03， 由蒸馏水配制而成， 其总体积 为 lLo
本发明中， 步骤 (2)中用 NaOH或 HCL调节混合液 PH值为中性。
本发明的有益效果是：
( 1 )提出了一种提高蛋白质生物产氢的方法，将蛋白质的紫外变性和生物产氢结合起来， 使蛋白质转化率和氢气产量分别提高 2.79倍和 2.99倍。
( 2 )蛋白质紫外照射预处理有利于蛋白质去折叠使其构象改变、结构松散进而增加发酵 阶段蛋白酶的切入点， 有利于蛋白质的生物利用和氢气的产生。相对于其它蛋白质变性方法， 紫外线预处理无残留和二次污染， 优势明显。
( 3 )相对于酸性或碱性发酵条件， 在中性 pH下提高蛋白质的转化率和氢气产量， 可以 大大减少蛋白质废水处理过程中的药剂费用， 同时可以减轻发酵设备的酸碱腐蚀。 附图说明
图 1为本发明蛋白质废水的紫外预处理装置。
图中标号： 1为紫外灯镇流器， 2为循环冷却水， 3为蛋白质溶液， 4为石英管， 5为紫 外灯， 6为磁力搅拌器转子， 7为磁力搅拌器。 具体实施方式
下面结合实例作进一步详细说明， 应当理解下面所举的实例只是为了解释说明本发明， 并不包括本发明的所有内容。
下列实例中蛋白质废水的紫外预处理装置如图 1所示， 紫外照射蛋白质废水时采用浸没 式水内照射， 同时打开磁力搅拌器和外部循环冷却水， 紫外照射一定时间后得到预处理后的 蛋白质废水。
实施例 1
将 300mL COD为 5000mg/L、 NaHC03 5g/L、 K2HP03 0.183g/L的蛋白质废水不进行紫外 预处理， 直接加入到厌氧反应器内做空白参照， 接种加热处理 （102°C、 30min ) 后的厌氧活 性污泥使反应器内的污泥浓度（SS )为 4000 ± 200mg/L，再加入 1ml的微量元素和 0.02% ( 6(^L) 体积比的三氯甲烷后，用 NaOH或 HCL调节混合物的 pH为 7 ± 0. 2 ,经氮气吹扫反应器 2min 后用橡胶塞密封使其保持厌氧状态， 并将反应器放入温度为 36士 1 °C、 转速为 140 ± 2rpm的 摇床内厌氧发酵一定时间， 每 12h测定一次反应器内的氢气体积和氢气含量， 并在整个过程 中通过 NaOH或 HCL维持反应器内溶液 pH为中性。
发酵结束后， 将混合物 4500rpm 离心 15mi n 得到上清液， 测得上清液中挥发酸总量为 950.2mgCOD/L; 发酵 84h后累积氢气产量为 19.6mIJg-COD。 实施例 2
将和实例 1相同的蛋白质废水加入如图 1所示的紫外预处理装置中， 采用浸没式水内照 射， 保持紫外线照射强度为 14w/L废水， 水层厚度为 3cm; 同时打开磁力搅拌器和循环冷却 水， 使紫外线照射过程中蛋白质废水的温度维持在 20~25 °C， 紫外照射 0.5~5h后得到预处理 后的蛋白质废水， 其性质如表 1所示。
将 300mL紫外预处理 2h的蛋白质废水加入到厌氧反应器内进行发酵产氢， 其它操作如 实例 1。 发酵结束后， 将混合物 4500rpm离心 15min得到上清液， 测得上清液中挥发酸总量 为 3600.4mgCOD/L; 发酵 84h后累积氢气产量为 78.2mL/g-COD。
表 1紫外照射前后蛋白质废水的性质对比
指标 a 空白 UV 0.5h UV lh UV 2h UV 5h
COD 4960土 40 4960土 40 4940土 30 4920土 20 4910+30
VFAs 9.8 19.7 22.5 24.9 25.2
顧 4+-N N.D. N.D. N.D. N.D. N.D.
280nm吸光度 0.207 0.357 0.475 0632 0.844
COD、 VFAs 的单位是 mg-COD/L， NH4 +-N 的单位是 mg/L; 280nm吸光度是 溶液稀释 10倍后的数值， 无量纲。
实施例 3
将蛋白质废水加入到紫外预处理装置中， 保持紫外线照射强度为 lOw/L废水， 水层厚度 为 2cm， 紫外照射 0.5h。 再将 300mL预处理后的溶液加入到厌氧反应器内进行发酵产氢， 其 它操作如实例 2。 发酵结束后， 测得上清液中挥发酸总量为 1965.4mgCOD/L; 发酵 84h后累 积氢气产量为 45.5mIJg-COD。 实施例 4
将蛋白质废水加入到紫外预处理装置中， 保持紫外线照射强度为 40w/L废水， 水层厚度 为 10cm， 紫外照射 0.5h。 再将 300mL预处理后的溶液加入到厌氧反应器内进行发酵产氢， 其它操作如实例 2。 发酵结束后， 测得上清液中挥发酸总量为 1678.4mgCOD/L; 发酵 72h后 累积氢气产量为 39.2mL/g-COD。 实施例 5
将蛋白质废水加入到紫外预处理装置中， 保持紫外线照射强度为 lOw/L废水， 水层厚度 为 10cm， 紫外照射 10h。再将 300mL预处理后的溶液加入到厌氧反应器内进行发酵产氢， 其 它操作如实例 2。 发酵结束后， 测得上清液中挥发酸总量为 2746.3mgCOD/L; 发酵 84h后累 积氢气产量为 57.2mIJg-COD。 实施例 6
将蛋白质废水加入到紫外预处理装置中， 保持紫外线照射强度为 14w/L废水， 水层厚度 为 3cm， 紫外照射 2h。再将 300mL预处理后的溶液加入到厌氧反应器内进行发酵产氢， 加入 0.01% (30μυ 的三氯甲烷抑制同型产乙酸菌， 其它操作如实例 2。 发酵结束后测得上清液中 挥发酸总量为 3557.9mgCOD/L; 发酵 84h后累积氢气产量为 75.1mL/g-COD。 实施例 7
将蛋白质废水加入到紫外预处理装置中， 保持紫外线照射强度为 14w/L废水， 水层厚度 为 3cm， 紫外照射 2h。再将 300mL预处理后的溶液加入到厌氧反应器内进行发酵产氢， 加入 0.05% ( 15CVL) 的三氯甲烷抑制同型产乙酸菌， 其它操作如实例 2。 发酵结束后测得上清液 中挥发酸总量为 3540.3mgCOD/L; 发酵 96h后累积氢气产量为 77.0mL/g-COD。

Claims

权 利 要 求 书
1、 一种提高蛋白质废水生物产氢的方法， 其特征在于具体步骤如下：
( 1 )： 蛋白质废水紫外线照射预处理
将蛋白质废水加入紫外预处理装置中， 打开带有镇流器的紫外灯， 采用浸没式水内照射， 保持紫外线照射强度为 10~40w/L废水， 水层厚度为 2~10cm， 同时打开磁力搅拌器和循环冷却 水， 使紫外线照射过程中蛋白质废水的温度维持在 20~25°C， 紫外照射 0.5~10h; 得到预处理 后的蛋白质废水；
(2)： 预处理后的蛋白质废水在中性 pH条件下生物产氢
将步骤 (1)得到的预处理后的蛋白质废水加入到厌氧反应器内，接种加热处理后的厌氧活性 污泥， 使厌氧反应器内的活性污泥浓度 （SS ) 为 3500_4500mg/L， 再加入微量元素和三氯甲烷 后，调节混合物的 pH为中性，经氮气吹扫厌氧反应器 2min后用橡胶塞密封使其保持厌氧状态， 并将厌氧反应器在中温条件下，在摇床内厌氧发酵 72~96h，每 12h测定一次厌氧反应器内的氢 气体积和氢气含量， 并在整个过程中维持厌氧反应器内溶液 pH为中性； 其中： 三氯甲烷添加 量为蛋白质废水体积的 0.01%~0.05%， 微量元素加入量为蛋白质废水体积的 0.33%。
2、 根据权利要求 1所述的一种提高蛋白质废水生物产氢的方法， 其特征在于步骤 （1 ) 中 蛋白质废水的紫外照射时间为 l~3h， 水层厚度为 2~4cm。
3、 根据权利要求 1所述的一种提高蛋白质废水生物产氢的方法， 其特征在于步骤 （2) 中 三氯甲烷添加量为蛋白质废水体积的 0.02%~0.03%。
4、 根据权利要求 1所述的一种提高蛋白质废水生物产氢的方法， 其特征在于加热处理后 的厌氧活性污泥为 102 °C加热煮沸 30min的污泥。
5、 根据权利要求 1所述的一种提高蛋白质废水生物产氢的方法， 其特征在于步骤 (2)中所 述每 1L微量元素溶液中含有 2.0g的 EDTA-2Na、 2.0g的 FeS04.7H20、 O.lg的 H3B03、 O.lg的 CoCl 6H20、 O.lg的 ZnCl2、 0.05g的 Cu (Ν03)2·5Η20、 O.lg的 MnCl 4H20、 0.75g的 Na2Mo04、
0.02g的 NiCl 6H20和 O.OOlg的 Na2Se03， 由蒸馏水配制而成， 其总体积为 1L。
6、 根据权利要求 1所述的一种提高蛋白质废水生物产氢的方法， 其特征在于步骤 (2)中用
NaOH或 HCL调节混合液 PH值为中性。
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