CN103204613B - Method for extracting phosphorus in phosphorus containing chemical-biological mixed sludge - Google Patents
Method for extracting phosphorus in phosphorus containing chemical-biological mixed sludge Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 149
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000011574 phosphorus Substances 0.000 title claims abstract description 148
- 239000010802 sludge Substances 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 claims abstract description 28
- 239000006228 supernatant Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 159000000014 iron salts Chemical class 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000029087 digestion Effects 0.000 abstract description 44
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 9
- 239000005416 organic matter Substances 0.000 abstract description 8
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 7
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000010979 pH adjustment Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010865 sewage Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum salt Chemical class 0.000 description 3
- 230000001079 digestive effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009294 enhanced biological phosphorus removal Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 150000004666 short chain fatty acids Chemical class 0.000 description 2
- 235000021391 short chain fatty acids Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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Abstract
本发明涉及一种提取含磷化学-生物混合污泥中磷元素的方法，属于从剩余污泥中回收磷元素的技术领域，包括以下步骤：将含磷化学-生物混合污泥放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；调节并维持剩余污泥的pH值为2～8，密闭反应器，在30～50℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。与现有技术相比，对于含磷酸铝或磷酸铁的混合污泥，维持pH值为2～8能释出混合污泥中60～80％的磷，比不调pH时高出10～30％；同时此条件下能使有机物(以溶解性有机碳计)的溶出比不调pH高25～60％；本发明能提高化学-生物混合污泥厌氧消化的释磷率，同时又利于有机物的释放和污泥减量，对污泥资源化和减量化意义重大。The invention relates to a method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, which belongs to the technical field of recovering phosphorus from excess sludge, and comprises the following steps: placing phosphorus-containing chemical-biological mixed sludge in a reactor Settling at room temperature for 24 hours, draining the supernatant to obtain excess sludge; adjusting and maintaining the pH value of the excess sludge at 2-8, closing the reactor, anaerobic digestion at 30-50°C for 7 days, Then both biological phosphorus and chemical phosphorus in the phosphorus-containing chemical-biological mixed sludge are released. Compared with the prior art, for mixed sludge containing aluminum phosphate or iron phosphate, maintaining a pH value of 2-8 can release 60-80% of phosphorus in the mixed sludge, which is 10-30% higher than that without pH adjustment. %; under this condition, the stripping of organic matter (in terms of dissolved organic carbon) can be made 25% to 60% higher than that without adjusting the pH; The release of organic matter and the reduction of sludge are of great significance to the resource utilization and reduction of sludge.
Description
技术领域technical field
本发明涉及一种从剩余污泥中回收磷元素的技术，尤其是涉及一种提取含磷化学-生物混合污泥中磷元素的方法。The invention relates to a technique for recovering phosphorus from excess sludge, in particular to a method for extracting phosphorus from phosphorus-containing chemical-biological mixed sludge.
背景技术Background technique
磷是动植物生长不可缺少的无机营养元素，在生物体原生质的组成和新陈代谢中起到了重要作用，磷矿石作为一种不可再生的自然资源正变得越来越稀缺，开采的代价也越来越高。磷在人类生产、使用之后大部分进入污水中，不妥善处理会导致水体富营养化，破坏水环境。目前，污水中磷的去除主要通过生物强化除磷工艺(EBPR)将水体中的磷元素转移到污泥中，通过剩余污泥的排出达到从污水中除磷的目的，但是受进水碳源、溶解氧、硝酸盐、污泥龄等多种因素影响，EBPR工艺运行并不稳定。为了达到《城镇污水处理厂污染物排放标准》(GB 18918-2002)一级A排放标准(TP≤0.5mg/L)，化学辅助除磷工艺在污水处理厂得到广泛应用，化学除磷过程产生了大量化学污泥且含磷量较高。无论是生物除磷工艺还是化学除磷工艺，最终污水中的大部分磷元素都富集在剩余污泥中，国内外的调查表明污水经过处理后，约85％的磷进入污泥中，没有强化除磷工艺的污水厂剩余污泥中磷元素所占比例约为2～4％，采用强化除磷工艺的污水厂剩余污泥含磷率能达到5～13％。Phosphorus is an indispensable inorganic nutrient element for the growth of animals and plants, and plays an important role in the composition and metabolism of the protoplasm of organisms. Phosphorus rock, as a non-renewable natural resource, is becoming more and more scarce, and the cost of mining is getting higher and higher. come higher. After human production and use, most of phosphorus enters the sewage. If it is not properly treated, it will lead to eutrophication of the water body and damage the water environment. At present, the removal of phosphorus in sewage is mainly through the bio-enhanced phosphorus removal process (EBPR), which transfers the phosphorus in the water to the sludge, and the purpose of phosphorus removal from the sewage is achieved through the discharge of the remaining sludge. , Dissolved oxygen, nitrate, sludge age and other factors, the operation of EBPR process is not stable. In order to meet the "Pollutant Discharge Standards for Urban Sewage Treatment Plants" (GB 18918-2002) Class A discharge standard (TP≤0.5mg/L), chemical assisted phosphorus removal process is widely used in sewage treatment plants, chemical phosphorus removal process produces A large amount of chemical sludge with high phosphorus content. Whether it is a biological phosphorus removal process or a chemical phosphorus removal process, most of the phosphorus in the final sewage is enriched in the remaining sludge. Investigations at home and abroad show that after the sewage is treated, about 85% of the phosphorus enters the sludge. The proportion of phosphorus element in the residual sludge of the sewage plant with the enhanced phosphorus removal process is about 2-4%, and the phosphorus content rate of the residual sludge of the sewage plant with the enhanced phosphorus removal process can reach 5-13%.
厌氧消化处理是实现剩余污泥稳定化、减量化和资源化最广泛采用的手段。通过厌氧消化不仅可以产生大量的短链脂肪酸(SCFAs)或者甲烷，而且还能减少剩余污泥产量，起到污泥减量化作用，在碱性条件下污泥厌氧消化的减量百分比能达到40～60％。同时剩余污泥厌氧消化过程中还会释放大量的氮、磷元素，对消化液中氨氮、正磷酸盐的回收利用既可以减少人类对自然界磷矿的开采，又可以减少消化液回流时高浓度氨氮和正磷酸盐对脱氮除磷工艺带来的影响。Anaerobic digestion is the most widely used method to achieve the stabilization, reduction and resource utilization of excess sludge. Anaerobic digestion can not only produce a large amount of short-chain fatty acids (SCFAs) or methane, but also reduce the output of excess sludge and play a role in sludge reduction. The percentage reduction of sludge anaerobic digestion under alkaline conditions It can reach 40-60%. At the same time, a large amount of nitrogen and phosphorus elements will be released during the anaerobic digestion of excess sludge. The recycling of ammonia nitrogen and orthophosphate in the digestive juice can not only reduce the mining of natural phosphate rock by humans, but also reduce the high temperature when the digestive juice is refluxed. Effects of concentrated ammonia nitrogen and orthophosphate on nitrogen and phosphorus removal processes.
目前国内外已有采用厌氧消化回收剩余污泥中碳源和氮磷元素的专利，大部分研究主要集中在生物污泥上，而对于回收含磷化学-生物混合污泥中的磷元素，提高磷回收效率的研究鲜有报道，也没有相关的专利。由于化学辅助除磷工艺在城市污水处理厂的广泛应用，研究厌氧消化过程中化学磷和生物磷的释放，提高消化液中的磷含量，对后期氮磷的资源化具有非常重要的现实意义和经济价值。At present, there are domestic and foreign patents on the use of anaerobic digestion to recover carbon sources and nitrogen and phosphorus elements in excess sludge. Most of the research is mainly focused on biological sludge, and for the recovery of phosphorus in phosphorus-containing chemical-biological mixed sludge, There are few reports on improving the efficiency of phosphorus recovery, and there are no related patents. Due to the wide application of chemical-assisted phosphorus removal technology in urban sewage treatment plants, it is of great practical significance to study the release of chemical phosphorus and biological phosphorus in the anaerobic digestion process and increase the phosphorus content in the digestive juice for the resource utilization of nitrogen and phosphorus in the later stage. and economic value.
发明内容Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种既能释放生物磷又能释放化学磷的提取含磷化学-生物混合污泥中磷元素的方法。The object of the present invention is to provide a method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge that can release both biological phosphorus and chemical phosphorus in order to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put the phosphorus-containing chemical-biological mixed sludge in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge;
(2)调节并维持剩余污泥的pH值为2～8，密闭反应器，在30～50℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Adjust and maintain the pH value of the remaining sludge at 2-8, close the reactor, and anaerobically digest it at 30-50°C for 7 days, then release the biological phosphorus in the phosphorus-containing chemical-biological mixed sludge The chemical phosphorus is also released.
步骤(2)所述的调节并维持剩余污泥的pH值所采用的原料为6～15mol/L的氢氧化钠溶液和4～6mol/L的盐酸溶液。The raw materials used for adjusting and maintaining the pH value of the excess sludge in step (2) are 6-15 mol/L sodium hydroxide solution and 4-6 mol/L hydrochloric acid solution.
步骤(1)所述的含磷化学-生物混合污泥为投加铝盐或铁盐进行化学辅助除磷处理后的污泥。The phosphorus-containing chemical-biological mixed sludge described in step (1) is the sludge after adding aluminum salt or iron salt for chemically assisted phosphorus removal treatment.
当步骤(1)所述的含磷化学-生物混合污泥为投加铝盐进行化学辅助除磷处理后的污泥时，步骤(2)中要调节并维持剩余污泥的pH值为2～5；When the phosphorus-containing chemical-biological mixed sludge described in step (1) is the sludge after chemically assisted phosphorus removal treatment by adding aluminum salts, the pH value of the remaining sludge should be adjusted and maintained at 2 in step (2). ~5;
当步骤(1)所述的含磷化学-生物混合污泥为投加铁盐进行化学辅助除磷处理后的污泥时，步骤(2)中要调节并维持剩余污泥的pH值为6～8。When the phosphorus-containing chemical-biological mixed sludge described in step (1) is the sludge after chemically assisted phosphorus removal by adding iron salts, the pH value of the remaining sludge should be adjusted and maintained at 6 in step (2). ~8.
本发明既能释放生物磷又能释放其化学磷的厌氧消化技术是同时考虑pH值对剩余污泥厌氧消化过程中生物磷的影响与pH值对化学磷沉淀释磷的影响。The anaerobic digestion technology capable of releasing biological phosphorus and chemical phosphorus in the present invention simultaneously considers the influence of pH value on biological phosphorus in the anaerobic digestion process of excess sludge and the influence of pH value on the precipitation and release of chemical phosphorus.
在进行厌氧消化的过程中，使用pH计监测反应器中pH的变化，并调节并维持pH在特定范围内。During the process of anaerobic digestion, use a pH meter to monitor the change of pH in the reactor, and adjust and maintain the pH within a specific range.
本发明的技术原理为：酸碱条件下污泥厌氧消化过程中，微生物细胞不能维持平衡渗透压而被破坏，促进胞内物质溶出，使厌氧消化上清液中有机物、氮磷浓度增加。而化学磷在厌氧消化过程中由于维持的pH不同或者化学物质与污泥中有机物的反应，会有不同程度的释磷。由此可知，维持pH在一定的范围内对含化学磷的剩余污泥进行厌氧消化，能同时利于微生物细胞的释磷和化学污泥的释磷，从而提高厌氧消化上清液中的磷浓度。The technical principle of the present invention is: in the process of anaerobic digestion of sludge under acid-base conditions, microbial cells cannot maintain a balanced osmotic pressure and are destroyed, promote the dissolution of intracellular substances, and increase the concentration of organic matter, nitrogen and phosphorus in the supernatant of anaerobic digestion . In the process of anaerobic digestion, chemical phosphorus will release phosphorus to varying degrees due to the different pH maintained or the reaction between chemical substances and organic matter in sludge. It can be seen that maintaining the pH within a certain range for anaerobic digestion of excess sludge containing chemical phosphorus can simultaneously facilitate the release of phosphorus from microbial cells and phosphorus from chemical sludge, thereby increasing the concentration of phosphorus in the supernatant of anaerobic digestion. Phosphorus concentration.
与现有技术相比，本发明具有以下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1)本方法能同时使生物污泥中的磷与化学污泥中的磷释放，提高上清液中的磷浓度，有利于提高后期氮磷资源的回收率，实现对剩余污泥的资源化利用。(1) This method can release the phosphorus in the biological sludge and the phosphorus in the chemical sludge at the same time, increase the phosphorus concentration in the supernatant, help to improve the recovery rate of nitrogen and phosphorus resources in the later stage, and realize the resource recovery of the remaining sludge utilization.
(2)该方法条件下，厌氧消化7天内，总悬浮固体(TSS)的减量百分比能达到15～30％，包括挥发性悬浮固体(VSS)的减量和部分无机物的溶解，从而减少了剩余污泥的处置量。(2) Under the method conditions, within 7 days of anaerobic digestion, the percentage reduction of total suspended solids (TSS) can reach 15-30%, including the reduction of volatile suspended solids (VSS) and the dissolution of some inorganic substances, thereby Reduced disposal of excess sludge.
(3)本方法条件下，将含磷化学-生物混合污泥厌氧消化，与纯生物污泥厌氧消化相比，上清液中有机物的溶出、挥发酸的产生规律基本一致，厌氧消化过程中，均能使污泥中的有机物释出，不影响后续有机物产酸和产甲烷。(3) Under the conditions of this method, the phosphorus-containing chemical-biological mixed sludge is anaerobically digested. Compared with the anaerobic digestion of pure biological sludge, the dissolution of organic matter in the supernatant and the production of volatile acids are basically the same. During the digestion process, the organic matter in the sludge can be released without affecting the subsequent acid and methane production of the organic matter.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。The present invention will be described in detail below in conjunction with specific embodiments.
实施例1Example 1
(1)分别取400mL浓缩后的纯生物污泥(总悬浮固体浓度为11.5g/L，挥发性悬浮固体浓度为8.5g/L)加入不同的反应器中，用6mol/L的盐酸溶液和6mol/L的氢氧化钠溶液维持厌氧消化过程中pH＝3，同时做不控制pH值的生物污泥厌氧消化试验，充氮气0.5min，密闭反应器在35℃条件下厌氧消化7天。(1) Take 400mL concentrated pure biological sludge (total suspended solids concentration is 11.5g/L, volatile suspended solids concentration is 8.5g/L) into different reactors, use 6mol/L hydrochloric acid solution and 6mol/L sodium hydroxide solution maintains pH=3 during the anaerobic digestion process, and at the same time, do anaerobic digestion test of biological sludge without controlling the pH value, fill with nitrogen for 0.5min, and conduct anaerobic digestion in a closed reactor at 35°C for 7 sky.
分别取400mL浓缩后含铝盐的混合污泥加入不同的反应器中，进行厌氧消化试验，试验方法同上。Take 400mL of concentrated aluminum-salt-containing mixed sludge and put them into different reactors for anaerobic digestion test. The test method is the same as above.
(2)每24h取1次样，测两种污泥厌氧消化上清液中正磷酸盐、溶解性有机碳(STOC)、挥发性脂肪酸(VFA)的浓度。(2) Take a sample every 24 hours to measure the concentration of orthophosphate, dissolved organic carbon (STOC) and volatile fatty acid (VFA) in the anaerobic digestion supernatant of the two kinds of sludge.
(3)厌氧消化7天后测TSS浓度和VSS浓度。(3) Measure TSS concentration and VSS concentration after 7 days of anaerobic digestion.
(4)对比纯生物污泥与含铝盐的混合污泥厌氧消化上清液中的正磷酸盐浓度，可以看出维持pH＝3能使混合污泥中的生物磷和化学磷均有释放，而不调pH时磷酸铝中的磷不能释出。通过公式(1)、(2)、(3)可以计算出不同pH条件下混合污泥总的释磷率，其中包括生物污泥的释磷率和化学磷的释磷率。(4) Comparing the concentration of orthophosphate in the anaerobic digestion supernatant of pure biological sludge and mixed sludge containing aluminum salts, it can be seen that maintaining pH=3 can make both biological phosphorus and chemical phosphorus in mixed sludge The phosphorus in aluminum phosphate cannot be released when the pH is not adjusted. The total phosphorus release rate of mixed sludge under different pH conditions can be calculated by formulas (1), (2) and (3), including the phosphorus release rate of biological sludge and the phosphorus release rate of chemical phosphorus.
其中：PT—混合污泥中泥水总磷的浓度，以PO4 3-P计，mg/L；Among them: P T - the concentration of total phosphorus in mud water in mixed sludge, calculated as PO 4 3- P, mg/L;
PML——合污泥厌氧消化上清液中的PO4 3--P浓度，mg/L；P ML - PO 4 3- -P concentration in the supernatant of anaerobic digestion of combined sludge, mg/L;
PBL——生物污泥厌氧消化上清液中的PO4 3--P浓度，mg/L；P BL - PO 4 3- -P concentration in the anaerobic digestion supernatant of biological sludge, mg/L;
维持pH＝3，纯生物污泥厌氧消化上清液中正磷酸盐浓度比不控制pH高出20％；对于磷酸铝，维持pH＝3比不控制pH值释磷率高5％；综合纯生物污泥与化学污泥，维持pH＝3混合污泥的释磷率比不控制pH值高出25％，能释出混合污泥总磷中70～80％的磷，其中生物污泥释磷70％，磷酸铝的释磷率为5％。Maintaining pH=3, the concentration of orthophosphate in the anaerobic digestion supernatant of pure biological sludge was 20% higher than that without pH control; for aluminum phosphate, maintaining pH=3 was 5% higher than that without controlling pH value; comprehensive pure For biological sludge and chemical sludge, the phosphorus release rate of the mixed sludge maintained at pH=3 is 25% higher than that without pH value control, and 70-80% of the total phosphorus in the mixed sludge can be released, of which the biological sludge released Phosphorus is 70%, and the phosphorus release rate of aluminum phosphate is 5%.
(5)厌氧消化7天后测得TSS浓度表明，不控制pH值厌氧消化7天能使含磷酸铝的混合污泥中TSS减量5％，维持pH＝3能使混合污泥中TSS减量13％。(5) The TSS concentration measured after 7 days of anaerobic digestion shows that the anaerobic digestion without controlling the pH value for 7 days can reduce the TSS in the mixed sludge containing aluminum phosphate by 5%, and maintaining pH=3 can make the TSS in the mixed sludge 13% reduction.
(6)对比纯生物污泥与含磷酸铝的混合污泥厌氧消化上清液中的STOC、VFA的浓度，相同pH条件下，两种污泥在厌氧消化过程中释出的有机物浓度基本相同。与不控制pH值相比，维持pH＝3混合污泥厌氧消化上清液中STOC浓度比不控制pH高50％。(6) Comparing the concentration of STOC and VFA in the anaerobic digestion supernatant of pure biological sludge and mixed sludge containing aluminum phosphate, under the same pH conditions, the concentration of organic matter released by the two sludges during anaerobic digestion basically the same. Compared with not controlling the pH value, the concentration of STOC in the anaerobic digestion supernatant of mixed sludge maintained at pH=3 was 50% higher than that without pH control.
实施例2Example 2
(1)分别取400mL浓缩后的纯生物污泥(总悬浮固体浓度为10.8g/L，挥发性悬浮固体浓度为8.1g/L)加入不同的反应器中，用6mol/L的盐酸溶液和6mol/L的氢氧化钠溶液维持厌氧消化过程中pH＝7，充氮气0.5min，密闭反应器在35℃条件下厌氧消化7天。(1) Take 400mL concentrated pure biological sludge (the concentration of total suspended solids is 10.8g/L, the concentration of volatile suspended solids is 8.1g/L) into different reactors, and use 6mol/L hydrochloric acid solution and 6 mol/L sodium hydroxide solution maintained pH=7 during the anaerobic digestion process, filled with nitrogen for 0.5 min, and anaerobically digested in a closed reactor at 35°C for 7 days.
分别取400mL浓缩后含磷酸铁的混合污泥加入不同的反应器中，进行厌氧消化试验，试验方法同上。Take 400mL of concentrated ferric phosphate-containing mixed sludge and put them into different reactors for anaerobic digestion test. The test method is the same as above.
(2)每24h取1次样，测两种污泥厌氧消化上清液中正磷酸盐、STOC、VFA浓度。(2) Take a sample every 24 hours, and measure the concentration of orthophosphate, STOC and VFA in the anaerobic digestion supernatant of the two kinds of sludge.
(3)混合污泥厌氧消化7天后测TSS和VSS浓度。(3) The concentrations of TSS and VSS were measured after 7 days of anaerobic digestion of mixed sludge.
(4)同实施例1，利用公式(1)、(2)、(3)可以计算出混合污泥总的释磷率，其中包括生物污泥的释磷率和磷酸铁的释磷率。(4) With embodiment 1, utilize formula (1), (2), (3) to calculate the total phosphorus release rate of mixed sludge, including the phosphorus release rate of biological sludge and the phosphorus release rate of ferric phosphate.
对比纯生物污泥与含磷酸铁的混合污泥厌氧消化上清液中的正磷酸盐浓度，可以看出维持pH＝7能释放混合污泥中80％的磷，其中生物污泥释磷率为70％，磷酸铁释磷率为10％左右。Comparing the orthophosphate concentration in the anaerobic digestion supernatant of pure biological sludge and mixed sludge containing iron phosphate, it can be seen that maintaining pH = 7 can release 80% of the phosphorus in the mixed sludge, of which the biological sludge releases phosphorus The rate is 70%, and the release rate of iron phosphate is about 10%.
(5)含磷酸铁的混合污泥厌氧消化7天后测得TSS浓度与VSS浓度表明，维持pH＝7能使含磷酸铁的混合污泥中TSS减量5％，VSS减量10％左右。(5) The TSS concentration and VSS concentration measured after 7 days of anaerobic digestion of mixed sludge containing iron phosphate showed that maintaining pH=7 can reduce TSS by 5% and VSS by about 10% in mixed sludge containing iron phosphate .
(6)对比纯生物污泥与含磷酸铁的混合污泥厌氧消化上清液中的STOC、VFA的浓度，维持pH＝7时含磷酸铁的混合污泥在厌氧消化上清液中STOC、VFA浓度与纯生物污泥厌氧消化上清液中相差不大。(6) Contrast the concentration of STOC and VFA in the anaerobic digestion supernatant of the pure biological sludge and the mixed sludge containing iron phosphate, and maintain pH=7 when the mixed sludge containing iron phosphate is in the anaerobic digestion supernatant The concentration of STOC and VFA was not much different from that in the anaerobic digestion supernatant of pure biological sludge.
实施例3Example 3
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铝盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding aluminum salt) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge mud;
(2)采用6mol/L的氢氧化钠溶液和4mol/L的盐酸溶液调节并维持剩余污泥的pH值为2，密闭反应器，在30℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 6mol/L sodium hydroxide solution and 4mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 2, close the reactor, and perform anaerobic digestion at 30°C for 7 days, then both The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
实施例4Example 4
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铝盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding aluminum salt) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge mud;
(2)采用15mol/L的氢氧化钠溶液和6mol/L的盐酸溶液调节并维持剩余污泥的pH值为5，密闭反应器，在50℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 15mol/L sodium hydroxide solution and 6mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 5, close the reactor, and anaerobically digest it at 50°C for 7 days, then both The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
实施例5Example 5
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铝盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding aluminum salt) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge mud;
(2)采用10mol/L的氢氧化钠溶液和5mol/L的盐酸溶液调节并维持剩余污泥的pH值为4，密闭反应器，在40℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 10mol/L sodium hydroxide solution and 5mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 4, close the reactor, and anaerobically digest it at 40°C for 7 days, then both The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
实施例6Example 6
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铁盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding iron salts) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge. mud;
(2)采用6mol/L的氢氧化钠溶液和4mol/L的盐酸溶液调节并维持剩余污泥的pH值为6，密闭反应器，在30℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 6mol/L sodium hydroxide solution and 4mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 6, close the reactor, and anaerobically digest it at 30°C for 7 days, then both The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
实施例7Example 7
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铁盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding iron salts) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge. mud;
(2)采用15mol/L的氢氧化钠溶液和6mol/L的盐酸溶液调节并维持剩余污泥的pH值为8，密闭反应器，在50℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 15mol/L sodium hydroxide solution and 6mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 8, close the reactor, anaerobic digestion at 50°C for 7 days, then release The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
实施例8Example 8
一种提取含磷化学-生物混合污泥中磷元素的方法，该方法包括以下步骤：A method for extracting phosphorus in phosphorus-containing chemical-biological mixed sludge, the method comprising the following steps:
(1)将含磷化学-生物混合污泥(为投加铁盐进行化学辅助除磷处理后的污泥)放在反应器内，在室温下静沉24h，排出上清液，得到剩余污泥；(1) Put phosphorus-containing chemical-biological mixed sludge (sludge after chemically assisted phosphorus removal treatment by adding iron salts) in the reactor, let it settle at room temperature for 24 hours, and discharge the supernatant to obtain the remaining sludge. mud;
(2)采用9mol/L的氢氧化钠溶液和5mol/L的盐酸溶液调节并维持剩余污泥的pH值为7，密闭反应器，在40℃条件下厌氧消化7天，则既释放出含磷化学-生物混合污泥中的生物磷又释放出化学磷。(2) Use 9mol/L sodium hydroxide solution and 5mol/L hydrochloric acid solution to adjust and maintain the pH value of the remaining sludge at 7, close the reactor, and anaerobically digest it at 40°C for 7 days, then both The biological phosphorus in the phosphorus-containing chemical-biological mixed sludge releases chemical phosphorus.
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