CN104478519B - The device and method of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution - Google Patents

The device and method of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution Download PDF

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CN104478519B
CN104478519B CN201410787213.3A CN201410787213A CN104478519B CN 104478519 B CN104478519 B CN 104478519B CN 201410787213 A CN201410787213 A CN 201410787213A CN 104478519 B CN104478519 B CN 104478519B
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valve
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algae
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CN104478519A (en
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朱伟
张会文
龚淼
李明
包建平
肖曼
代晓炫
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Hohai University HHU
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    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05BPHOSPHATIC FERTILISERS
    • C05B17/00Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

本发明涉及一种以蓝藻藻液的超临界水气化产物回收氮磷的装置及方法,属于资源环境领域。本发明利用超临界水的特性将打捞上岸的蓝藻藻液直接进行气化处理后,回收液相产物中富集的藻液中大量氨氮、活性磷成分,生成MAP晶体作为作为农作物肥料施用,解决蓝藻传统处理工艺中脱水能耗高、处理周期长、资源化水平低下等问题,实现蓝藻快速处理后有效回收。本发明提供的方法实现了两个“同步回收”,同步回收蓝藻中氮磷,及同步回收超临界水气化液相和固相中的P元素,由于P元素多赋存于固相残留中,通过固相残留中P形态的转化进入液相,进而能获得90%左右的高氮磷回收效率。

The invention relates to a device and a method for recovering nitrogen and phosphorus from a supercritical water gasification product of cyanobacteria liquid, belonging to the field of resources and environment. The invention utilizes the characteristics of supercritical water to directly gasify the cyanobacteria liquid salvaged ashore, recover a large amount of ammonia nitrogen and active phosphorus components in the algae liquid enriched in the liquid phase product, and generate MAP crystals to be used as crop fertilizers, solving the problem of In the traditional treatment process of cyanobacteria, there are problems such as high dehydration energy consumption, long treatment cycle, and low level of resource utilization, etc., and effective recovery of cyanobacteria can be achieved after rapid treatment. The method provided by the present invention realizes two "synchronous recovery", synchronous recovery of nitrogen and phosphorus in cyanobacteria, and synchronous recovery of P element in supercritical water gasification liquid phase and solid phase, because P element mostly exists in solid phase residue , through the transformation of the P form in the solid phase residue into the liquid phase, and then a high nitrogen and phosphorus recovery efficiency of about 90% can be obtained.

Description

以蓝藻藻液的超临界水气化产物回收氮磷的装置及方法Device and method for recovering nitrogen and phosphorus from supercritical water gasification product of cyanobacteria liquid

技术领域technical field

本发明属于资源环境领域,具体涉及一种以蓝藻藻液的超临界水气化产物回收氮磷的装置及方法。The invention belongs to the field of resources and environment, and in particular relates to a device and a method for recovering nitrogen and phosphorus from a supercritical water gasification product of cyanobacteria liquid.

背景技术Background technique

水体富营养化而暴发蓝藻形成水华已对我国环境造成严重的危害。打捞是消除内陆水体水华污染重要且常见的措施,在我国滇池、太湖、巢湖等已广泛应用。据不完全统计,2011年江苏省从太湖累计打捞藻液97万吨,比2010年打捞量增加近30万吨。而这些打捞上岸的藻液,如何及时、快速的无害化处理与利用,是水华蓝藻治理的关键。若对打捞的藻液不能及时、有效地无害化处理,藻液腐烂发臭后,氮、磷等养分释放进入水体而产生二次的环境污染,使得湖泊水华蓝藻持续性爆发。The eutrophication of water body and the outbreak of cyanobacteria to form algal blooms have caused serious harm to the environment of our country. Salvage is an important and common measure to eliminate algae bloom pollution in inland water bodies, and it has been widely used in Dianchi Lake, Taihu Lake, and Chaohu Lake in my country. According to incomplete statistics, Jiangsu Province salvaged 970,000 tons of algae liquid from Taihu Lake in 2011, nearly 300,000 tons more than in 2010. How to timely and quickly harmlessly treat and utilize these salvaged algae fluids is the key to the control of algal blooms. If the salvaged algae liquid cannot be treated in a timely and effective manner, after the algae liquid rots and stinks, nutrients such as nitrogen and phosphorus will be released into the water body and cause secondary environmental pollution, resulting in continuous outbreaks of cyanobacteria in lakes.

目前,申请号为200710025550.9的中国专利公开了一种以水华蓝藻为原料制备肥料的方法,该专利以堆肥方式将脱水蓝藻腐熟处理后,制成有机肥或有机无机复混肥,但要求脱水蓝藻的含水率达到20~40%、且处理时间长,这就需要耗费大量的能量和场地;申请号为20061009.5的中国专利公开了一种蓝藻沼气能源化发酵的方法及其产品,该专利提出了厌氧发酵方法处理打捞蓝藻进而获取沼气,但是不能改变处理时间长、效率低下等问题;申请号为201010520895.3的中国专利公开了一种利用超临界水氧化法处理蓝藻的系统和方法,该专利通过对蓝藻以超临界水氧化的方式进行处理,最后形成CO2和H2O,实现蓝藻无害化处理;而本专利则利用超临界水部分氧化水气化技术将藻液中的氮磷转化入液相产物,然后利用MAP法高效回收藻液中的氮磷,并突破MAP法仅适用于液相回收的局限,通过酸洗震荡转化回收固相残留物质中大量的P元素。At present, the Chinese patent application No. 200710025550.9 discloses a method for preparing fertilizers from water bloom cyanobacteria. The patent dehydrates the dehydrated cyanobacteria in a composting manner to make organic fertilizer or organic-inorganic compound fertilizer, but dehydration is required. The water content of cyanobacteria reaches 20-40%, and the processing time is long, which requires a lot of energy and space; the Chinese patent application number 20061009.5 discloses a method and product of cyanobacteria biogas energy fermentation, which proposes The anaerobic fermentation method is used to treat the salvaged cyanobacteria and then obtain biogas, but the problems such as long processing time and low efficiency cannot be changed; the Chinese patent application number 201010520895.3 discloses a system and method for treating cyanobacteria using supercritical water oxidation. By treating cyanobacteria with supercritical water oxidation, and finally forming CO 2 and H 2 O, the harmless treatment of cyanobacteria is realized; and this patent uses supercritical water partial oxidation water gasification technology to remove nitrogen and phosphorus in algae liquid Transform into liquid phase products, and then use the MAP method to efficiently recover nitrogen and phosphorus in the algae liquid, and break through the limitation that the MAP method is only suitable for liquid phase recovery, and recover a large amount of P elements in the solid phase residual material through acid washing and shaking conversion.

发明内容Contents of the invention

解决的技术问题:本发明的目的是克服现有技术的不足而提供一种以蓝藻藻液的超临界水气化产物回收氮磷的装置及方法,利用超临界水的特性将打捞上岸的蓝藻藻液直接进行气化处理后,回收液相产物中富集的藻液中大量氨氮、活性磷成分,生成MAP晶体(又称鸟粪石)作为作为农作物肥料施用,解决蓝藻传统处理工艺中脱水能耗高、处理周期长、资源化水平低下等问题,实现蓝藻快速处理后有效回收。Technical problem to be solved: the purpose of this invention is to overcome the deficiencies in the prior art and provide a device and method for recovering nitrogen and phosphorus from the supercritical water gasification product of cyanobacteria liquid, and use the characteristics of supercritical water to salvage the cyanobacteria ashore. After the algae liquid is directly gasified, a large amount of ammonia nitrogen and active phosphorus components in the enriched algae liquid in the liquid phase product are recovered, and MAP crystals (also known as struvite) are generated and used as crop fertilizers to solve dehydration in the traditional treatment process of cyanobacteria High energy consumption, long processing cycle, low level of resource utilization, etc., to achieve effective recycling of blue-green algae after rapid processing.

本发明的技术方案:Technical scheme of the present invention:

将湖泊水华时打捞上来的蓝藻藻液中含有大量的氮磷元素,是一种良好的资源。本发明将藻液通过超临界水气化处理,将其中大部分的氮磷转移到液相产物中,再通过MAP法生成MAP晶体进行高效回收利用。The cyanobacteria liquid salvaged during the lake bloom contains a large amount of nitrogen and phosphorus elements, which is a good resource. In the invention, the supercritical water gasification process is performed on the algae liquid, and most of the nitrogen and phosphorus are transferred to the liquid phase product, and then the MAP crystal is generated by the MAP method for efficient recycling.

以蓝藻藻液的超临界水气化产物回收氮磷的装置,包括贮存罐,进口阀,高压柱塞泵,出口阀,热交换器,气液流量阀,气液分离器罐,湿式气体流量计,液体流量计,背压阀,超临界反应器,MAP反应罐,低速搅拌电机M,氯化镁贮存槽,磷酸二氢钾贮存槽,系统压力调节阀,氯化镁控制阀,磷酸二氢钾控制阀,氯化镁定量给料机D,磷酸二氢钾定量给料机D,干烘间,pH在线监测仪,调控池,MAP晶体输送阀,固相振荡器,酸液贮存槽,酸液控制阀,酸液定量计D,酸液输出阀;其中,贮存罐的第一输出管依次通过进口阀、高压柱塞泵、出口阀与热交换器的第一输入管相连,热交换器的第一输出管通过背压阀与超临界反应器的输入管连接,超临界反应器的第一输出管通过系统压力调节阀与热交换器的第二输入管相连,超临界反应器的第二输出管通过控制阀与固相振荡器的第一输入管相连,酸液贮存槽依次通过酸液控制阀、酸液定量计D与固相振荡器的第二输入管相连,固相振荡器的第一输出管通过酸液输出阀与超临界反应器的输入管相连,固相振荡器的第二输出管输出固相产物;A device for recovering nitrogen and phosphorus from supercritical water gasification products of cyanobacteria liquid, including storage tanks, inlet valves, high-pressure plunger pumps, outlet valves, heat exchangers, gas-liquid flow valves, gas-liquid separator tanks, wet gas flow meter, liquid flow meter, back pressure valve, supercritical reactor, MAP reaction tank, low-speed stirring motor M, magnesium chloride storage tank, potassium dihydrogen phosphate storage tank, system pressure regulating valve, magnesium chloride control valve, potassium dihydrogen phosphate control valve , Magnesium chloride quantitative feeder D, potassium dihydrogen phosphate quantitative feeder D, drying room, pH online monitor, regulation pool, MAP crystal delivery valve, solid-phase oscillator, acid storage tank, acid control valve, Acid liquid quantitative meter D, acid liquid output valve; wherein, the first output pipe of the storage tank is connected with the first input pipe of the heat exchanger through the inlet valve, high-pressure plunger pump, and outlet valve in sequence, and the first output pipe of the heat exchanger The pipe is connected with the input pipe of the supercritical reactor through the back pressure valve, the first output pipe of the supercritical reactor is connected with the second input pipe of the heat exchanger through the system pressure regulating valve, and the second output pipe of the supercritical reactor is passed through The control valve is connected with the first input pipe of the solid-phase oscillator, the acid liquid storage tank is connected with the second input pipe of the solid-phase oscillator through the acid liquid control valve and the acid quantitative meter D successively, and the first output pipe of the solid-phase oscillator is The tube is connected to the input tube of the supercritical reactor through the acid liquid output valve, and the second output tube of the solid phase oscillator outputs the solid phase product;

热交换器的第二输出管通过气液流量阀与气液分离器罐的输入管相连,气液分离器罐的第一输出管通过湿式气体流量计与干烘间的第一输入管相连,气液分离器罐的第二输出管通过液体流量计与MAP反应罐的输入管相连,氯化镁贮存槽依次通过氯化镁控制阀、氯化镁定量给料机D与MAP反应罐的输入管相连,磷酸二氢钾贮存槽依次通过磷酸二氢钾控制阀、磷酸二氢钾定量给料机D与MAP反应罐的输入管相连,MAP反应罐的第一输出管通过MAP晶体输送阀与干烘间的第二输入管相连,干烘间的第一输出管输出气相产物,第二输出管输出成品肥料,MAP反应罐的第二输出管输出上清液,pH在线监测仪与调控池并联连接后通过管路插入MAP反应罐内,低速搅拌电机M的扇叶置于MAP反应罐内。The second output pipe of the heat exchanger is connected to the input pipe of the gas-liquid separator tank through the gas-liquid flow valve, and the first output pipe of the gas-liquid separator tank is connected to the first input pipe of the drying room through a wet gas flow meter. The second output pipe of the gas-liquid separator tank is connected to the input pipe of the MAP reaction tank through the liquid flow meter, and the magnesium chloride storage tank is connected to the input pipe of the MAP reaction tank through the magnesium chloride control valve and the magnesium chloride quantitative feeder D in turn, and the dihydrogen phosphate The potassium storage tank is connected to the input pipe of the MAP reaction tank through the potassium dihydrogen phosphate control valve and the potassium dihydrogen phosphate quantitative feeder D in sequence, and the first output pipe of the MAP reaction tank is connected to the second one of the drying room through the MAP crystal delivery valve. The input pipes are connected, the first output pipe of the drying room outputs the gas phase product, the second output pipe outputs the finished fertilizer, the second output pipe of the MAP reaction tank outputs the supernatant, and the pH on-line monitor is connected in parallel with the control tank and passes through the pipeline Insert it into the MAP reaction tank, and place the fan blade of the low-speed stirring motor M in the MAP reaction tank.

所述的以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,包括以下步骤:The method for reclaiming nitrogen and phosphorus in the water bloom cyanobacteria liquid by means of a device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid comprises the following steps:

1)将打捞上岸的蓝藻藻液,通过高压柱塞泵3打入超临界反应器,停留3-5分钟进行水气化反应;产物通过热交换器回收热量,回收的热量用于下一批蓝藻进样的预热处理;经过热交换器的产物经冷却降压后,进入气液分离器罐分离气液产物,获得富含氮磷的液相产物;固相产物在控制阀的调节下通过超临界反应器11的第二输出管进入固相振荡器后,酸液贮存槽中的酸液经酸液控制阀和酸液定量计D定量进入固相振荡器,震荡8h后上清液进入MAP反应罐;1) Put the salvaged cyanobacteria liquid into the supercritical reactor through the high-pressure plunger pump 3, stay for 3-5 minutes for water gasification reaction; the product recovers heat through the heat exchanger, and the recovered heat is used for the next batch Preheating treatment of cyanobacteria sampling; after cooling and reducing the pressure of the product passing through the heat exchanger, it enters the gas-liquid separator tank to separate the gas-liquid product, and obtains the liquid phase product rich in nitrogen and phosphorus; the solid phase product is adjusted by the control valve After entering the solid phase oscillator through the second output pipe of the supercritical reactor 11, the acid liquid in the acid liquid storage tank enters the solid phase oscillator quantitatively through the acid liquid control valve and the acid liquid quantitative meter D, and the supernatant after shaking for 8 hours Enter the MAP reaction tank;

2)超临界液相产物通过输送管道进入MAP反应罐中进行反应,通过pH在线监测仪和盛有碱液的调控池监控调节MAP反应罐中的酸碱环境;2) The supercritical liquid phase product enters the MAP reaction tank through the delivery pipeline for reaction, and monitors and regulates the acid-base environment in the MAP reaction tank through the pH online monitor and the regulating pool filled with lye;

3)将氯化镁和磷酸二氢钾干粉分别通过氯化镁定量给料机D和磷酸二氢钾定量给料机D输送进入MAP反应罐中,并由低速搅拌电机M搅拌溶解后参与MAP反应;3) The magnesium chloride and potassium dihydrogen phosphate dry powder are transported into the MAP reaction tank through the magnesium chloride quantitative feeder D and the potassium dihydrogen phosphate quantitative feeder D respectively, and are stirred and dissolved by the low-speed stirring motor M to participate in the MAP reaction;

4)反应后的上清液经MAP反应罐的第二输出管排出,并进行后处理,生成的MAP晶体沉淀通过MAP反应罐的第一输出管经由干烘间的第二输入管进入干烘间,由超临界水气化产生的气相产物中的余热烘干后,气相产物经干烘间的第一输出管输出,成品肥料经干烘间的第二输出管输出并收集作为农业肥料施用。4) After the reaction, the supernatant is discharged through the second output pipe of the MAP reaction tank, and is subjected to post-treatment, and the generated MAP crystal precipitation enters the drying room through the first output pipe of the MAP reaction tank through the second input pipe of the drying room. During the period, after the waste heat in the gas phase product produced by supercritical water gasification is dried, the gas phase product is output through the first output pipe of the drying room, and the finished fertilizer is output through the second output pipe of the drying room and collected as agricultural fertilizer for application .

所述的以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,其中,步骤1)中高压柱塞泵的压力设定为22MPa。The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid by using the device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid, wherein, the pressure of the high-pressure plunger pump in step 1) is set to 22MPa.

所述的以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,其中,步骤1)中将超临界反应器预先升温至450~500℃。The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid with a device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid, wherein, in step 1), the temperature of the supercritical reactor is raised to 450-500° C. in advance.

所述的以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,其中,步骤2)中MAP反应罐中的pH为9.0~10.7。The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid by using the device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid, wherein, the pH in the MAP reaction tank in step 2) is 9.0-10.7.

上述的以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,其中,所述酸液贮存槽中贮存的酸液为盐酸,所述固相振荡器采用序批式运行方式。The above-mentioned method for reclaiming nitrogen and phosphorus in the water bloom cyanobacteria liquid with the device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid, wherein, the acid liquid stored in the acid liquid storage tank is hydrochloric acid, and the solid phase The oscillator adopts the sequential batch mode of operation.

有益效果Beneficial effect

第一,本发明将打捞上岸富含氮磷的蓝藻藻液直接进行超临界水气化处理后,大量的氮磷反应后进入液相产物中,利用MAP反应将液相中的氮磷转化成固体肥料,提高肥效且便于后续的运输和施用;First, in the present invention, after the salvaged cyanobacteria liquid rich in nitrogen and phosphorus is directly subjected to supercritical water gasification treatment, a large amount of nitrogen and phosphorus enters the liquid phase product after the reaction, and the nitrogen and phosphorus in the liquid phase are converted into Solid fertilizer, which improves fertilizer efficiency and facilitates subsequent transportation and application;

第二,本发明整个反应过程无需二次脱水及水分调节带来的额外费用,且反应过程中无需额外添加氧化剂;Second, the entire reaction process of the present invention does not require additional costs caused by secondary dehydration and moisture adjustment, and no additional oxidant is added during the reaction process;

第三,本发明通过超临界水气化处理后进行MAP法回收氮磷能大大缩短反应时间,实现高效、快速的蓝藻处理;Third, the present invention recovers nitrogen and phosphorus by the MAP method after supercritical water gasification treatment, which can greatly shorten the reaction time and realize efficient and rapid cyanobacteria treatment;

第四,本发明提供的方法实现了两个“同步回收”,同步回收蓝藻中氮磷,及同步回收超临界水气化液相和固相中的P元素,由于P元素多赋存于固相残留中,本发明克服了常规回收方法只能回收液相中的氮磷元素的不足,通过固相残留中P形态的转化进入液相,进而能获得90%左右的高氮磷回收效率。Fourth, the method provided by the present invention realizes two "synchronous recovery", synchronous recovery of nitrogen and phosphorus in cyanobacteria, and synchronous recovery of P element in supercritical water gasification liquid phase and solid phase, because P element mostly occurs in solid In the phase residue, the present invention overcomes the deficiency that the conventional recovery method can only recover nitrogen and phosphorus elements in the liquid phase, and can obtain a high nitrogen and phosphorus recovery efficiency of about 90% through the conversion of the P form in the solid phase residue into the liquid phase.

附图说明Description of drawings

图1为本发明回收水华蓝藻藻液中氮磷的装置示意图,其中1是贮存罐,2是进口阀,3是高压柱塞泵,4是出口阀,5是热交换器,6是气液流量阀,7是气液分离器罐,8是湿式气体流量计,9是液体流量计,10是背压阀,11是超临界反应器,12是MAP反应罐,13是低速搅拌电机M,14是氯化镁贮存槽,15是磷酸二氢钾贮存槽,16是系统压力调节阀,17是氯化镁控制阀,18是磷酸二氢钾控制阀,19是氯化镁定量给料机D,20是磷酸二氢钾定量给料机D,21是干烘间,22是pH在线监测仪,23是调控池,24是MAP晶体输送阀,25是固相振荡器,26是酸液贮存槽,27是酸液控制阀,28是酸液定量计D,29是酸液输出阀,30是控制阀。Fig. 1 is the schematic diagram of the device for recovering nitrogen and phosphorus in the algae liquid of water bloom cyanobacteria of the present invention, wherein 1 is a storage tank, 2 is an inlet valve, 3 is a high-pressure plunger pump, 4 is an outlet valve, 5 is a heat exchanger, and 6 is a gas pump. Liquid flow valve, 7 is gas-liquid separator tank, 8 is wet gas flow meter, 9 is liquid flow meter, 10 is back pressure valve, 11 is supercritical reactor, 12 is MAP reaction tank, 13 is low-speed stirring motor M , 14 is magnesium chloride storage tank, 15 is potassium dihydrogen phosphate storage tank, 16 is system pressure regulating valve, 17 is magnesium chloride control valve, 18 is potassium dihydrogen phosphate control valve, 19 is magnesium chloride quantitative feeder D, 20 is phosphoric acid Dihydropotassium quantitative feeder D, 21 is the drying room, 22 is the pH online monitor, 23 is the control tank, 24 is the MAP crystal delivery valve, 25 is the solid phase oscillator, 26 is the acid storage tank, 27 is Acid liquid control valve, 28 is an acid liquid quantitative meter D, 29 is an acid liquid output valve, and 30 is a control valve.

具体实施方式detailed description

下面通过具体实施例对本发明作进一步详细说明,其中所述固相振荡器25采用序批式运行方式。The present invention will be further described in detail through specific examples below, wherein the solid-phase oscillator 25 adopts a sequential batch operation mode.

实施例1Example 1

结合图1,以蓝藻藻液的超临界水气化产物回收氮磷的装置,包括贮存罐1,进口阀2,高压柱塞泵3,出口阀4,热交换器5,气液流量阀6,气液分离器罐7,湿式气体流量计8,液体流量计9,背压阀10,超临界反应器11,MAP反应罐12,低速搅拌电机M13,氯化镁贮存槽14,磷酸二氢钾贮存槽15,系统压力调节阀16,氯化镁控制阀17,磷酸二氢钾控制阀18,氯化镁定量给料机D19,磷酸二氢钾定量给料机D20,干烘间21,pH在线监测仪22,调控池23,MAP晶体输送阀24,固相振荡器25,酸液贮存槽26,酸液控制阀27,酸液定量计D28,酸液输出阀29;其中,贮存罐1的第一输出管依次通过进口阀2、高压柱塞泵3、出口阀4与热交换器5的第一输入管相连,热交换器5的第一输出管通过背压阀10与超临界反应器11的输入管连接,超临界反应器11的第一输出管通过系统压力调节阀16与热交换器5的第二输入管相连,超临界反应器11的第二输出管通过控制阀30与固相振荡器25的第一输入管相连,酸液贮存槽26依次通过酸液控制阀27、酸液定量计D28与固相振荡器25的第二输入管相连,固相振荡器25的第一输出管通过酸液输出阀29与超临界反应器11的输入管相连,固相振荡器25的第二输出管输出固相产物;In conjunction with Figure 1, the device for recovering nitrogen and phosphorus with the supercritical water gasification product of cyanobacteria liquid includes a storage tank 1, an inlet valve 2, a high-pressure plunger pump 3, an outlet valve 4, a heat exchanger 5, and a gas-liquid flow valve 6 , gas-liquid separator tank 7, wet gas flow meter 8, liquid flow meter 9, back pressure valve 10, supercritical reactor 11, MAP reaction tank 12, low-speed stirring motor M13, magnesium chloride storage tank 14, potassium dihydrogen phosphate storage Tank 15, system pressure regulating valve 16, magnesium chloride control valve 17, potassium dihydrogen phosphate control valve 18, magnesium chloride quantitative feeder D19, potassium dihydrogen phosphate quantitative feeder D20, drying room 21, pH online monitor 22, Control tank 23, MAP crystal transfer valve 24, solid-phase oscillator 25, acid liquid storage tank 26, acid liquid control valve 27, acid liquid quantitative meter D28, acid liquid output valve 29; wherein, the first output pipe of storage tank 1 The inlet valve 2, the high-pressure plunger pump 3, and the outlet valve 4 are connected to the first input pipe of the heat exchanger 5 in sequence, and the first output pipe of the heat exchanger 5 is connected to the input pipe of the supercritical reactor 11 through the back pressure valve 10. Connect, the first outlet pipe of supercritical reactor 11 is connected with the second inlet pipe of heat exchanger 5 by system pressure regulating valve 16, the second outlet pipe of supercritical reactor 11 is connected with solid phase oscillator 25 by control valve 30 The acid liquid storage tank 26 is connected to the second input pipe of the solid-phase oscillator 25 through the acid liquid control valve 27 and the acid liquid quantitative meter D28 successively, and the first output pipe of the solid-phase oscillator 25 passes through the acid liquid. The liquid output valve 29 is connected with the input pipe of the supercritical reactor 11, and the second output pipe of the solid phase oscillator 25 outputs the solid phase product;

热交换器5的第二输出管通过气液流量阀6与气液分离器罐7的输入管相连,气液分离器罐7的第一输出管通过湿式气体流量计8与干烘间21的第一输入管相连,气液分离器罐7的第二输出管通过液体流量计9与MAP反应罐12的输入管相连,氯化镁贮存槽14依次通过氯化镁控制阀17、氯化镁定量给料机D19与MAP反应罐12的输入管相连,磷酸二氢钾贮存槽15依次通过磷酸二氢钾控制阀18、磷酸二氢钾定量给料机D20与MAP反应罐12的输入管相连,MAP反应罐12的第一输出管通过MAP晶体输送阀24与干烘间21的第二输入管相连,干烘间21的第一输出管输出气相产物,第二输出管输出成品肥料,MAP反应罐12的第二输出管输出上清液,pH在线监测仪22与调控池23并联连接后通过管路插入MAP反应罐12内,低速搅拌电机M13的扇叶置于MAP反应罐12内。The second output pipe of the heat exchanger 5 is connected to the input pipe of the gas-liquid separator tank 7 through the gas-liquid flow valve 6, and the first output pipe of the gas-liquid separator tank 7 passes through the connection between the wet gas flow meter 8 and the drying room 21. The first input pipe is connected, and the second output pipe of gas-liquid separator tank 7 is connected with the input pipe of MAP reaction tank 12 by liquid flowmeter 9, and magnesium chloride storage tank 14 passes through magnesium chloride control valve 17, magnesium chloride quantitative feeder D19 and The input pipe of MAP reaction tank 12 links to each other, potassium dihydrogen phosphate storage tank 15 links to each other with the input pipe of MAP reaction tank 12 successively by potassium dihydrogen phosphate control valve 18, potassium dihydrogen phosphate quantitative feeder D20, the MAP reaction tank 12 The first output pipe is connected with the second input pipe of the drying room 21 through the MAP crystal transfer valve 24, the first output pipe of the drying room 21 outputs the gas phase product, the second output pipe outputs the finished fertilizer, and the second output pipe of the MAP reaction tank 12 The output pipe outputs the supernatant, and the online pH monitor 22 is connected in parallel with the regulating tank 23 and inserted into the MAP reaction tank 12 through the pipeline, and the fan blade of the low-speed stirring motor M13 is placed in the MAP reaction tank 12 .

实施例2Example 2

以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,包括以下步骤:The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid by means of a device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid comprises the following steps:

1)打捞上岸的蓝藻藻液(含水率98%~99%)进入贮存罐1,藻水分离后待处理。1) The salvaged cyanobacteria algae liquid (with a water content of 98% to 99%) enters the storage tank 1, and the algae water is separated to be treated.

2)试验开始时,打开高压柱塞泵的进口阀2,开启高压柱塞泵3,并打开热交换器5的加热装置,使其温度上升至300℃左右,开启超临界反应器11,升温至500℃。2) When the test starts, open the inlet valve 2 of the high-pressure plunger pump, turn on the high-pressure plunger pump 3, and turn on the heating device of the heat exchanger 5 to make its temperature rise to about 300 ° C, open the supercritical reactor 11, and heat up to 500°C.

3)打开藻液出口阀4,使藻水分离后的藻液进入热交换器5,通过热交换器升温至250℃;然后通过背压阀10进入超临界反应器11,在反应器内将温度达到400℃,压力25Mpa,达到超临界状态,停留3分钟进行水气化反应;反应结束后,打开系统压力调节阀16,使气液混合相产物进入热交换器5,通过热交换器将下一阶段的待处理藻液升温至250℃,且过程中使得气液混合相产物温度降低,打开气液流量阀6进入气液分离器罐7,气液分离后获得可燃气体和富含氮磷的液相产物,并通过湿式气体流量计8,利用带有余热的气相产物于干烘间21将后续获得的肥料烘干制成成品。3) Open the algae liquid outlet valve 4, so that the algae liquid after the separation of the algae water enters the heat exchanger 5, and heats up to 250 ° C through the heat exchanger; then enters the supercritical reactor 11 through the back pressure valve 10, and the When the temperature reaches 400°C and the pressure is 25Mpa, it reaches a supercritical state, and stays for 3 minutes to carry out the water gasification reaction; after the reaction, open the system pressure regulating valve 16, so that the gas-liquid mixed phase product enters the heat exchanger 5, through which the The algae liquid to be treated in the next stage is heated to 250°C, and the temperature of the gas-liquid mixed phase product is lowered during the process, and the gas-liquid flow valve 6 is opened to enter the gas-liquid separator tank 7. After gas-liquid separation, combustible gas and nitrogen-rich The liquid phase product of phosphorus is passed through the wet gas flow meter 8, and the gas phase product with waste heat is used to dry the subsequent obtained fertilizer in the drying room 21 to make a finished product.

4)超临界反应结束后,无机固相产物由超临界反应器11底部排出进入固相振荡器25,打开酸液控制阀27,通过酸液定量计D28定量输入盐酸溶液,震荡停留8h后,打开酸液输出阀29,使上清液进入MAP反应罐12混合反应,固相振荡器25中的固相产物残渣定期清理排出。4) After the supercritical reaction ends, the inorganic solid phase product is discharged into the solid phase oscillator 25 by the bottom of the supercritical reactor 11, the acid liquid control valve 27 is opened, and the hydrochloric acid solution is quantitatively input by the acid liquid quantitative meter D28, and after the shock stays for 8 hours, Open the acid liquid output valve 29 to allow the supernatant liquid to enter the MAP reaction tank 12 for mixed reaction, and the solid phase product residue in the solid phase oscillator 25 is regularly cleaned and discharged.

5)液相产物经液体流量计9进入MAP反应罐12,通过pH在线监测仪22和盛有碱液的调控池23监控调节MAP反应罐12中的酸碱环境,维持MAP反应罐中的pH为9.0;将氯化镁和磷酸二氢钾干粉分别通过氯化镁定量给料机D19和磷酸二氢钾定量给料机D20输送进入MAP反应罐12中,并由低速搅拌电机M13搅拌溶解后参与MAP反应。5) The liquid phase product enters the MAP reaction tank 12 through the liquid flow meter 9, monitors and adjusts the acid-base environment in the MAP reaction tank 12 through the pH online monitor 22 and the regulating pool 23 filled with lye, and maintains the pH in the MAP reaction tank is 9.0; magnesium chloride and potassium dihydrogen phosphate dry powder are transported into the MAP reaction tank 12 through the magnesium chloride quantitative feeder D19 and the potassium dihydrogen phosphate quantitative feeder D20 respectively, and are stirred and dissolved by the low-speed stirring motor M13 to participate in the MAP reaction.

实施例3Example 3

以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,包括以下步骤:The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid by means of a device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid comprises the following steps:

1)打捞上岸的蓝藻藻液(含水率98%~99%)进入贮存罐1,藻水分离后待处理。1) The salvaged cyanobacteria algae liquid (with a water content of 98% to 99%) enters the storage tank 1, and the algae water is separated to be treated.

2)试验开始时,打开高压柱塞泵的进口阀2,开启高压柱塞泵3,并打开热交换器5的加热装置,使其温度上升至300℃左右,开启超临界反应器11,升温至500℃。2) When the test starts, open the inlet valve 2 of the high-pressure plunger pump, turn on the high-pressure plunger pump 3, and turn on the heating device of the heat exchanger 5 to make its temperature rise to about 300 ° C, open the supercritical reactor 11, and heat up to 500°C.

3)打开藻液出口阀4,使藻水分离后的藻液进入热交换器5,通过热交换器升温至250℃;然后通过背压阀10进入超临界反应器11,在反应器内将温度达到500℃,压力22Mpa,达到超临界状态,停留5分钟进行水气化反应;反应结束后,打开系统压力调节阀16,使气液混合相产物进入热交换器5,通过热交换器将下一阶段的待处理藻液升温至250℃,且过程中使得气液混合相产物温度降低,打开气液流量阀6进入气液分离器罐7,气液分离后获得可燃气体和富含氮磷的液相产物,并通过湿式气体流量计8,利用带有余热的气相产物于干烘间21将后续获得的肥料烘干制成成品。3) Open the algae liquid outlet valve 4, so that the algae liquid after the separation of the algae water enters the heat exchanger 5, and heats up to 250 ° C through the heat exchanger; then enters the supercritical reactor 11 through the back pressure valve 10, and the When the temperature reaches 500°C and the pressure is 22Mpa, it reaches a supercritical state, and stays for 5 minutes for water gasification reaction; after the reaction is completed, open the system pressure regulating valve 16, so that the gas-liquid mixed phase product enters the heat exchanger 5, and through the heat exchanger The algae liquid to be treated in the next stage is heated to 250°C, and the temperature of the gas-liquid mixed phase product is lowered during the process, and the gas-liquid flow valve 6 is opened to enter the gas-liquid separator tank 7. After gas-liquid separation, combustible gas and nitrogen-rich The liquid phase product of phosphorus is passed through the wet gas flow meter 8, and the gas phase product with waste heat is used to dry the subsequent obtained fertilizer in the drying room 21 to make a finished product.

4)超临界反应结束后,无机固相产物由超临界反应器11底部排出进入固相振荡器25,打开酸液控制阀27,通过酸液定量计D 28定量输入盐酸溶液,震荡停留8h后,打开酸液输出阀29,使上清液进入MAP反应罐12混合反应,固相振荡器25中的固相产物残渣定期清理排出。4) After the supercritical reaction ends, the inorganic solid phase product is discharged into the solid phase oscillator 25 by the bottom of the supercritical reactor 11, the acid liquid control valve 27 is opened, and the hydrochloric acid solution is quantitatively input by the acid liquid quantitative meter D 28, and after the shock stays for 8 hours , open the acid liquid output valve 29, so that the supernatant liquid enters the MAP reaction tank 12 for mixed reaction, and the solid phase product residue in the solid phase oscillator 25 is regularly cleaned and discharged.

5)液相产物经液体流量计9进入MAP反应罐12,通过pH在线监测仪22和盛有碱液的调控池23监控调节MAP反应罐12中的酸碱环境,维持MAP反应罐中的pH为10.7;将氯化镁和磷酸二氢钾干粉分别通过氯化镁定量给料机D19和磷酸二氢钾定量给料机D20输送进入MAP反应罐12中,并由低速搅拌电机M13搅拌溶解后参与MAP反应。5) The liquid phase product enters the MAP reaction tank 12 through the liquid flow meter 9, monitors and adjusts the acid-base environment in the MAP reaction tank 12 through the pH online monitor 22 and the regulating pool 23 filled with lye, and maintains the pH in the MAP reaction tank is 10.7; magnesium chloride and potassium dihydrogen phosphate dry powder are transported into the MAP reaction tank 12 through the magnesium chloride quantitative feeder D19 and the potassium dihydrogen phosphate quantitative feeder D20 respectively, and are stirred and dissolved by the low-speed stirring motor M13 to participate in the MAP reaction.

实施例4Example 4

以蓝藻藻液的超临界水气化产物回收氮磷的装置回收水华蓝藻藻液中氮磷的方法,包括以下步骤:The method for recovering nitrogen and phosphorus in the water bloom cyanobacteria liquid by means of a device for recovering nitrogen and phosphorus from the supercritical water gasification product of the cyanobacteria liquid comprises the following steps:

1)打捞上岸的蓝藻藻液(含水率98%~99%)进入贮存罐1,藻水分离后待处理。1) The salvaged cyanobacteria algae liquid (with a water content of 98% to 99%) enters the storage tank 1, and the algae water is separated to be treated.

2)试验开始时,打开高压柱塞泵的进口阀2,开启高压柱塞泵3,并打开热交换器5的加热装置,使其温度上升至300℃左右,开启超临界反应器11,升温至500℃。2) When the test starts, open the inlet valve 2 of the high-pressure plunger pump, turn on the high-pressure plunger pump 3, and turn on the heating device of the heat exchanger 5 to make its temperature rise to about 300 ° C, open the supercritical reactor 11, and heat up to 500°C.

3)打开藻液出口阀4,使藻水分离后的藻液进入热交换器5,通过热交换器升温至250℃;然后通过背压阀10进入超临界反应器11,在反应器内将温度达到450℃,压力22Mpa,达到超临界状态,停留5分钟进行水气化反应;反应结束后,打开系统压力调节阀16,使气液混合相产物进入热交换器5,通过热交换器将下一阶段的待处理藻液升温至250℃,且过程中使得气液混合相产物温度降低,打开气液流量阀6进入气液分离器罐7,气液分离后获得可燃气体和富含氮磷的液相产物,并通过湿式气体流量计8,利用带有余热的气相产物于干烘间21将后续获得的肥料烘干制成成品。3) Open the algae liquid outlet valve 4, so that the algae liquid after the separation of the algae water enters the heat exchanger 5, and heats up to 250 ° C through the heat exchanger; then enters the supercritical reactor 11 through the back pressure valve 10, and the The temperature reaches 450°C, the pressure is 22Mpa, and reaches a supercritical state, and stays for 5 minutes for water gasification reaction; after the reaction is completed, open the system pressure regulating valve 16, so that the gas-liquid mixed phase product enters the heat exchanger 5, and through the heat exchanger The algae liquid to be treated in the next stage is heated to 250°C, and the temperature of the gas-liquid mixed phase product is lowered during the process, and the gas-liquid flow valve 6 is opened to enter the gas-liquid separator tank 7. After gas-liquid separation, combustible gas and nitrogen-rich The liquid phase product of phosphorus is passed through the wet gas flow meter 8, and the gas phase product with waste heat is used to dry the subsequent obtained fertilizer in the drying room 21 to make a finished product.

4)超临界反应结束后,无机固相产物由超临界反应器11底部排出进入固相振荡器25,打开酸液控制阀27,通过酸液定量计D 28定量输入盐酸溶液,震荡停留8h后,打开酸液输出阀29,使上清液进入MAP反应罐12混合反应,固相振荡器25中的固相产物残渣定期清理排出。4) After the supercritical reaction ends, the inorganic solid phase product is discharged into the solid phase oscillator 25 by the bottom of the supercritical reactor 11, the acid liquid control valve 27 is opened, and the hydrochloric acid solution is quantitatively input by the acid liquid quantitative meter D 28, and after the shock stays for 8 hours , open the acid liquid output valve 29, so that the supernatant liquid enters the MAP reaction tank 12 for mixed reaction, and the solid phase product residue in the solid phase oscillator 25 is regularly cleaned and discharged.

5)液相产物经液体流量计9进入MAP反应罐12,通过pH在线监测仪22和盛有碱液的调控池23监控调节MAP反应罐12中的酸碱环境,维持MAP反应罐中的pH为9.0~10.7;将氯化镁和磷酸二氢钾干粉分别通过氯化镁定量给料机D19和磷酸二氢钾定量给料机D20输送进入MAP反应罐12中,并由低速搅拌电机M13搅拌溶解后参与MAP反应。5) The liquid phase product enters the MAP reaction tank 12 through the liquid flow meter 9, monitors and adjusts the acid-base environment in the MAP reaction tank 12 through the pH online monitor 22 and the regulating pool 23 filled with lye, and maintains the pH in the MAP reaction tank 9.0 to 10.7; the magnesium chloride and potassium dihydrogen phosphate dry powder are transported into the MAP reaction tank 12 through the magnesium chloride quantitative feeder D19 and the potassium dihydrogen phosphate quantitative feeder D20 respectively, and are stirred and dissolved by the low-speed stirring motor M13 to participate in the MAP reaction.

应用例1Application example 1

将太湖打捞上岸的进入藻水分离站的藻液,含水率为96%、TN及TP浓度分别为3268mg/L、180.63mg/L,经过500℃、5min的超临界水气化处理后进入MAP反应罐进行反应,充分搅拌后停留10分钟,沉淀进入干烘间烘干后获得成品肥料性质如表1所示。The algae liquid salvaged from Taihu Lake and entering the algae water separation station has a water content of 96%, TN and TP concentrations of 3268mg/L and 180.63mg/L respectively, and enters the MAP after being treated by supercritical water gasification at 500°C for 5 minutes React in the reaction tank, and stay for 10 minutes after fully stirring. After the precipitate is dried in the drying room, the properties of the finished fertilizer obtained are shown in Table 1.

应用例2Application example 2

将太湖打捞上岸的进入藻水分离站的藻液,通过脱水装置进步脱水浓缩藻液浓度,含水率降低至86%,TN及TP浓度分别为10008mg/L、544.93mg/L,经过500℃、5min的超临界水气化处理后进入MAP反应罐进行反应,充分搅拌后停留20分钟,沉淀进入干烘间烘干后获得成品肥料性质如表1所示。The algae liquid salvaged from Taihu Lake and entering the algae water separation station is dehydrated and concentrated through the dehydration device to increase the concentration of the dehydrated and concentrated algae liquid, and the water content is reduced to 86%. After 5 minutes of supercritical water gasification treatment, it enters the MAP reaction tank for reaction, fully stirs and stays for 20 minutes, and precipitates into the drying room for drying to obtain the properties of the finished fertilizer as shown in Table 1.

表1 获得的成品肥料的性质Table 1 Properties of the finished fertilizers obtained

通过超临界水处理后,利用MAP方法回收打捞藻液中氮磷的方法,一方面为降低富营养化湖泊中的氮、磷营养盐水平,解决了打捞蓝藻的出路问题,极短的反应处理时间和停留时间可更为自如应对蓝藻暴发时巨大的产生量,2011年累计从太湖打捞含水率98%左右的蓝藻97万吨,相当于直接从湖体取出氮近500吨,磷100吨,超临界水气化处理后进行MAP回收氮磷的方法可以快速高效实现打捞蓝藻的无害化处理和资源化利用;After supercritical water treatment, the MAP method is used to recover the nitrogen and phosphorus in the salvaged algae liquid. On the one hand, in order to reduce the nitrogen and phosphorus nutrient levels in eutrophic lakes, it solves the problem of salvaging blue-green algae, and the extremely short reaction process The time and residence time can be more flexible to cope with the huge production of blue-green algae outbreaks. In 2011, a total of 970,000 tons of blue-green algae with a water content of about 98% were salvaged from Taihu Lake, which is equivalent to nearly 500 tons of nitrogen and 100 tons of phosphorus directly from the lake. The method of recovering nitrogen and phosphorus by MAP after supercritical water gasification treatment can quickly and efficiently realize the harmless treatment and resource utilization of salvaged cyanobacteria;

另一方面,本发明将打捞蓝藻中的氮磷转化成可利用的农业肥料,转化效率快速高效,转化效率可达90%,远高于现有的仅回收液相产物中的P元素回收方法,缓解氮磷肥料生产过程中的经济成果、环境污染,以及日渐枯竭的磷矿石资源,如若将2011年太湖打捞的蓝藻中氮磷全部进行MAP回收,约可获得8500吨MAP晶体肥料;降低河湖内部污染负荷的同时,实现了一定经济效益,缓解了P矿石资源的枯竭和肥料生产过程中的环境污染。On the other hand, the present invention converts the nitrogen and phosphorus in salvaged blue-green algae into usable agricultural fertilizers, and the conversion efficiency is fast and efficient, and the conversion efficiency can reach 90%, which is much higher than the existing P element recovery method that only recovers liquid phase products , to alleviate the economic achievements, environmental pollution, and depleted phosphate rock resources in the production process of nitrogen and phosphorus fertilizers. If all the nitrogen and phosphorus in the cyanobacteria salvaged in Taihu Lake in 2011 are recovered by MAP, about 8,500 tons of MAP crystal fertilizers can be obtained; reduce While reducing the internal pollution load of rivers and lakes, certain economic benefits have been achieved, and the depletion of P ore resources and environmental pollution during fertilizer production have been alleviated.

Claims (4)

1. the device of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution, it is characterised in that including hold-up tank(1), enter Mouth valve(2), high-pressure plunger pump(3), outlet valve(4), heat exchanger(5), gas-liquid flow valve(6), gas-liquid separator tank(7), it is wet Formula gas flowmeter(8), fluid flowmeter(9), counterbalance valve(10), supercritical reaction device(11), MAP retort(12), low speed Stirring motor M(13), magnesium chloride storagetank(14), potassium dihydrogen phosphate storagetank(15), system pressure regulating valve(16), magnesium chloride Control valve(17), potassium dihydrogen phosphate control valve(18), magnesium chloride constant feeder D(19), potassium dihydrogen phosphate constant feeder D (20), do between drying(21), pH on-line computing models(22), regulate and control pond(23), MAP crystal transfer valves(24), solid phase oscillator(25), Acid solution storagetank(26), sour hydraulic control valve(27), acid solution quantitative scoring D(28), acid solution delivery valve(29), control valve(30);Wherein, Hold-up tank(1)The first efferent duct pass sequentially through inlet valve(2), high-pressure plunger pump(3), outlet valve(4)With heat exchanger(5)'s First input pipe is connected, heat exchanger(5)The first efferent duct pass through counterbalance valve(10)With supercritical reaction device(11)Input Pipe is connected, supercritical reaction device(11)The first efferent duct pass through system pressure regulating valve(16)With heat exchanger(5)Second Input pipe is connected, supercritical reaction device(11)The second efferent duct by controlling valve(30)With solid phase oscillator(25)It is first defeated Enter pipe to be connected, acid solution storagetank(26)Pass sequentially through sour hydraulic control valve(27), acid solution quantitative scoring D(28)With solid phase oscillator(25) The second input pipe be connected, solid phase oscillator(25)The first efferent duct pass through acid solution delivery valve(29)With supercritical reaction device (11)Input pipe be connected, solid phase oscillator(25)The second efferent duct output solid product;
Heat exchanger(5)The second efferent duct pass through gas-liquid flow valve(6)With gas-liquid separator tank(7)Input pipe be connected, gas Liquid/gas separator tank(7)The first efferent duct pass through wet gas flow meter(8)Between dry baking(21)The first input pipe be connected, gas Liquid/gas separator tank(7)The second efferent duct pass through fluid flowmeter(9)With MAP retort(12)Input pipe be connected, magnesium chloride Storagetank(14)Pass sequentially through magnesium chloride control valve(17), magnesium chloride constant feeder D(19)With MAP retort(12)Input Pipe is connected, potassium dihydrogen phosphate storagetank(15)Pass sequentially through potassium dihydrogen phosphate control valve(18), potassium dihydrogen phosphate constant feeder D (20)With MAP retort(12)Input pipe be connected, MAP retort(12)The first efferent duct pass through MAP crystal transfer valves (24)Between dry baking(21)The second input pipe be connected, do dry between(21)The first efferent duct output gas-phase product, second output Pipe exports finished product fertilizer, MAP retort(12)The second efferent duct output supernatant, pH on-line computing models(22)With regulation and control pond (23)MAP retort is inserted by pipeline after being connected in parallel(12)It is interior, stirring at low speed motor M(13)Flabellum be placed in MAP reaction Tank(12)It is interior.
2. the device that the supercritical water gasification product with blue-green algae algae solution described in claim 1 reclaims nitrogen phosphorus reclaims bloom blue algae algae The method of nitrogen phosphorus in liquid, it is characterised in that comprise the following steps:
1)The blue-green algae algae solution of moisture content 98% ~ 99% for salvaging disembarkation is entered into hold-up tank(1), it is pending after the separation of algae water;
2)The inlet valve of high-pressure plunger pump is opened during on-test(2), high-pressure plunger pump is opened, and open heat exchanger(5)'s Heater, 300 DEG C are risen to by its temperature, open supercritical reaction device(11)It is warming up to 450 ~ 500 DEG C;
3)Open algae solution outlet valve(4), the algae solution after the separation of algae water is entered heat exchanger(5), it is warming up to by heat exchanger 250℃;Then counterbalance valve is passed through(10)Into supercritical reaction device(11), 400 ~ 500 DEG C, pressure are reached in reactor temperature 22 ~ 25Mpa, reaches supercriticality, stops 3 ~ 5 minutes laggard water-filling gasification reactions;After reaction terminates, open system pressure and adjust Save valve(16), gas-liquid mixed phase product is entered heat exchanger(5), by heat exchanger by the pending algae solution liter of next stage Temperature to 250 DEG C, and during cause gas-liquid mixed phase product temperatur reduction, open gas-liquid flow valve(6)Into gas-liquid separator Tank(7), the liquid product of fuel gas and rich Nitrogen-and Phosphorus-containing is obtained after gas-liquid separation, and pass through wet gas flow meter(8), utilize Gas-phase product that band has surplus heat and it is dry dry between(21)Finished product is made in the fertilizer drying subsequently obtained;
4)After supercritical reaction terminates, inorganic solid phase product is by supercritical reaction device(11)Bottom is discharged into solid phase oscillator (25), open sour hydraulic control valve(27), pass through acid solution quantitative scoring D(28)Hydrochloric acid solution is quantitatively inputted, concussion is stopped after 8h, is opened Acid solution delivery valve(29), supernatant is entered MAP retort(12)Hybrid reaction, solid phase oscillator(25)In solid product it is residual Slag periodic cleaning is discharged;
5)Liquid product is through fluid flowmeter(9)Into MAP retort(12), pass through pH on-line computing models(22)With fill alkali lye Regulation and control pond(23)Monitoring regulation MAP retort(12)In acid or alkali environment, maintain MAP retort in pH be 9.0 ~ 10.7; Magnesium chloride and potassium dihydrogen phosphate dry powder are passed through into magnesium chloride constant feeder D respectively(19)With potassium dihydrogen phosphate constant feeder D (20)Deliver into MAP retort(12)In, and by stirring at low speed motor M(13)MAP reactions are participated in after stirring and dissolving.
3. the supercritical water gasification product according to claim 2 with blue-green algae algae solution reclaims the device recycle-water Chinese blue of nitrogen phosphorus The method of nitrogen phosphorus in algae algae solution, it is characterised in that the acid solution storagetank(26)The acid solution of middle storage is hydrochloric acid.
4. the supercritical water gasification product with blue-green algae algae solution according to Claims 2 or 3 reclaims the device recycle-water of nitrogen phosphorus The method of nitrogen phosphorus in Chinese blue algae algae solution, it is characterised in that the solid phase oscillator(25)Using sequencing batch operation mode.
CN201410787213.3A 2014-12-17 2014-12-17 The device and method of nitrogen phosphorus is reclaimed with the supercritical water gasification product of blue-green algae algae solution Expired - Fee Related CN104478519B (en)

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