CN114074930B - Method and device for preparing nitric acid - Google Patents
Method and device for preparing nitric acidDownload PDFInfo
- Publication number
- CN114074930B CN114074930BCN202110346065.1ACN202110346065ACN114074930BCN 114074930 BCN114074930 BCN 114074930BCN 202110346065 ACN202110346065 ACN 202110346065ACN 114074930 BCN114074930 BCN 114074930B
- Authority
- CN
- China
- Prior art keywords
- absorbent
- outlet
- gas
- inlet
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/40—Preparation by absorption of oxides of nitrogen
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/203—Preparation of nitrogen oxides using a plasma or an electric discharge
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Translated fromChinese技术领域technical field
本发明属于气体放电化学反应领域，涉及氮气氧化制备硝酸的方法及装置。The invention belongs to the field of gas discharge chemical reaction, and relates to a method and a device for preparing nitric acid by nitrogen oxidation.
背景技术Background technique
硝酸是用途广泛的重要基础化工原料，主要用于制造化肥、炸药和硝酸盐，此外也用于化纤、医药、染料、橡胶等制造过程。硝酸在工业上主要以氨氧化法生产，其工艺是将氨和空气的混合气通入灼热的铂铑合金网，在合金网的催化下，氨被氧化成一氧化氮(NO)，一氧化氮继续氧化为二氧化氮，随后被水溶液吸收制得硝酸。另外，也可采用电弧放电法，在约4000℃温度下合成氧化氮。但这些技术的主要缺点是工艺条件要求高，需要高温或高压，投资和运行成本高。Nitric acid is an important basic chemical raw material with a wide range of uses. It is mainly used in the manufacture of fertilizers, explosives, and nitrates. It is also used in the manufacturing processes of chemical fibers, medicines, dyes, and rubber. Nitric acid is mainly produced by ammonia oxidation in industry. The process is to pass the mixture of ammonia and air into the burning platinum-rhodium alloy mesh. Under the catalysis of the alloy mesh, ammonia is oxidized into nitric oxide (NO), nitric oxide Continue to be oxidized to nitrogen dioxide, and then absorbed by aqueous solution to produce nitric acid. In addition, the arc discharge method can also be used to synthesize nitrogen oxide at a temperature of about 4000 °C. However, the main disadvantages of these technologies are high process conditions, high temperature or high pressure, and high investment and operating costs.
由气体放电产生的非平衡等离子体(Nonthermal Plasma)作为一种促进化学反应的有效方法，已应用于结构稳定的有机物的降解和分子重组反应。该技术的主要优点是反应可在常温常压下进行，从而大大地节省了能量。中国发明专利(CN101244980 A)公开了气体放电一种甲烷与氯气反应转化为甲烷氯化物的方法。中国发明专利(CN106000079A)公开了固体氯化铁作为脱硝剂，通过氯化铁与一氧化氮之间的化学吸附反应去除气流中的氮氧化物的方法。As an effective method to promote chemical reactions, nonthermal plasma generated by gas discharge has been applied to the degradation and molecular recombination reactions of structurally stable organic substances. The main advantage of this technology is that the reaction can be carried out at normal temperature and pressure, which greatly saves energy. Chinese invention patent (CN101244980 A) discloses a gas discharge method in which methane reacts with chlorine to convert methane chloride. Chinese invention patent (CN106000079A) discloses the method that solid ferric chloride is used as a denitrification agent to remove nitrogen oxides in the gas stream through chemical adsorption reaction between ferric chloride and nitric oxide.
发明内容Contents of the invention
本发明的目的在于提供一种采用气体放电结合氯化铁吸收剂浆液吸收的方法来制备硝酸的方法应用于该方法的装置。The object of the present invention is to provide a kind of method that adopts the method that gas discharge combines iron chloride absorbent slurry to absorb to prepare the method for nitric acid and is applied to the device of this method.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明提供一种制备硝酸的方法，所述方法为：将包含氮气和氧气的混合气体(如空气，也可以是氮气和氧气的混合气体)干燥脱水后在气体放电反应吸收器中放电反应生成含一氧化氮的混合气体；与此同时导入吸收剂，吸收饱和后的吸收剂加入水或盐酸(对盐酸的浓度无特殊要求，一般质量浓度20％以下)脱吸再生，再生释放的一氧化氮气体经氧化、水或者质量分数30％以下的硝酸水溶液吸收后得到高浓度硝酸水溶液；所述吸收剂为氯化铁与水的混合物。The invention provides a method for preparing nitric acid, which comprises: drying and dehydrating a mixed gas containing nitrogen and oxygen (such as air, or a mixed gas of nitrogen and oxygen) and discharging it in a gas discharge reaction absorber to generate nitric acid Mixed gas containing nitric oxide; at the same time, introduce an absorbent, add water or hydrochloric acid (there is no special requirement for the concentration of hydrochloric acid, the general mass concentration is below 20%) to desorb and regenerate the saturated absorbent, and regenerate the released monoxide Nitrogen gas is oxidized, absorbed by water or nitric acid aqueous solution with a mass fraction of less than 30% to obtain a high-concentration nitric acid aqueous solution; the absorbent is a mixture of ferric chloride and water.
具体地，一种制备硝酸的方法，所述方法在如下装置中进行：Specifically, a method for preparing nitric acid, the method is carried out in the following device:
所述装置包括依次连接的干燥器(3)、气体放电反应吸收器(101)、物料储罐(102)、物料输送泵(12)、再生反应器(103)、抽气泵(14)与吸收塔(16)；以及控制上述各个部件及管道温度的温控系统；上述各个部件指气体放电反应吸收器(101)、物料储罐(102)、再生反应器(103)、吸收塔(16)；The device comprises a dryer (3), a gas discharge reaction absorber (101), a material storage tank (102), a material delivery pump (12), a regenerative reactor (103), an air pump (14) and an absorber connected in sequence. tower (16); and a temperature control system for controlling the above-mentioned components and pipeline temperature; the above-mentioned components refer to gas discharge reaction absorber (101), material storage tank (102), regeneration reactor (103), absorption tower (16) ;
所述干燥器(3)设有干燥器进口和干燥器出口，所述干燥器进口通过风机(2)连接气体进口(1)；The drier (3) is provided with a drier inlet and a drier outlet, and the drier inlet is connected to the gas inlet (1) through a fan (2);
所述气体放电反应吸收器(101)包括外接接地电极的导电筒体(4)、设置在所述导电筒体(4)顶端的浆液分布器(9)、贯穿所述浆液分布器(9)的中心电极棒(7)、设于所述导电筒体(10)上部的出气口(19)、设于所述导电筒体(10)底端的浆液循环槽(29)、设于所述浆液循环槽(29)底端的出液口(20)和设于导电筒体(4)上、所述出气口(19)和所述浆液循环槽(29)之间的进气口(18)；所述中心电极棒(7)与外接高压电源连接；所述出气口(19)通过净化器(6)与气体出口(5)连接；所述进气口(18)与所述干燥器出口连接；The gas discharge reaction absorber (101) includes a conductive cylinder (4) externally connected to a ground electrode, a slurry distributor (9) arranged at the top of the conductive cylinder (4), and a slurry distributor (9) passing through the slurry distributor (9). The center electrode rod (7), the air outlet (19) arranged on the upper part of the conductive cylinder (10), the slurry circulation tank (29) arranged at the bottom of the conductive cylinder (10), the slurry circulation tank (29) arranged on the slurry The liquid outlet (20) at the bottom of the circulation tank (29) and the air inlet (18) arranged on the conductive cylinder (4) between the air outlet (19) and the slurry circulation tank (29); The central electrode rod (7) is connected to an external high-voltage power supply; the gas outlet (19) is connected to the gas outlet (5) through a purifier (6); the air inlet (18) is connected to the outlet of the dryer ;
所述物料储罐(102)设有注浆口(28)、第一吸收剂进口(22)、第一吸收剂出口(24)、第一反应液进口(21)和第一反应液出口(23)；所述第一反应液进口(22)与所述出液口(20)连接，所述第一吸收剂出口(24)通过循环泵(10)与所述浆液分布器(9)连接；The material storage tank (102) is provided with a grouting port (28), a first absorbent inlet (22), a first absorbent outlet (24), a first reaction liquid inlet (21) and a first reaction liquid outlet ( 23); the first reaction liquid inlet (22) is connected to the liquid outlet (20), and the first absorbent outlet (24) is connected to the slurry distributor (9) through a circulation pump (10) ;
所述再生反应器(103)设有加液口(13)、第二反应液进口(25)、一氧化氮气体出口(26)和第二吸收剂出口(27)；所述第二反应液进口(25)通过再生物料泵(12)与所述第一反应液出口(23)连接，所述第二吸收剂出口(27)通过物料输送泵(12)与所述第一吸收剂进口(22)连接，所述一氧化氮气体出口(26)通过所述抽气泵(14)与所述吸收塔(16)(多级吸收塔，优选三级吸收塔)、尾气排出口(15)依次连接；The regenerative reactor (103) is provided with a liquid inlet (13), a second reaction liquid inlet (25), a nitric oxide gas outlet (26) and a second absorbent outlet (27); the second reaction liquid The inlet (25) is connected to the first reaction liquid outlet (23) through the regenerative material pump (12), and the second absorbent outlet (27) is connected to the first absorbent inlet ( 22) connected, the nitrogen monoxide gas outlet (26) is sequentially connected with the absorption tower (16) (multi-stage absorption tower, preferably three-stage absorption tower) and tail gas outlet (15) by the air pump (14) connect;
所述抽气泵(14)与所述吸收塔(16)之间的管道上还设有空压机(17)。An air compressor (17) is also provided on the pipeline between the air pump (14) and the absorption tower (16).
利用上述装置，所述方法包括以下步骤：Using the above-mentioned device, the method comprises the following steps:
(1)吸收剂从所述注浆口(28)加入所述物料储罐(102)中；所述吸收剂为氯化铁与水的混合物；(1) The absorbent is added into the material storage tank (102) from the grouting port (28); the absorbent is a mixture of ferric chloride and water;
(2)所述包含氮气和氧气的混合气体从所述气体进口(1)经过风机(2)进入所述干燥器(3)干燥(一般干燥至含水量1％以下，无特殊要求)后，从所述干燥器出口、进气口(18)进入所述气体放电反应吸收器(101)；(2) After the mixed gas containing nitrogen and oxygen enters the dryer (3) from the gas inlet (1) through the fan (2) for drying (generally dried to less than 1% water content, no special requirements), Enter the gas discharge reaction absorber (101) from the dryer outlet and air inlet (18);
(3)接通所述中心电极棒(7)的外接高压电源，所述中心电极棒(7)和导电筒体(4)之间空间发生气体放电，二氧化氮气和氢气被激发发生化学反应，得到含一氧化氮的混合气；与此同时，所述物料储罐(102)中的吸收剂经循环泵(10)输送到所述浆液分布器(9)后沿导电筒体(4)内壁流下，在所述浆液循环槽(29)中汇集，吸收了一氧化氮的吸收剂从所述浆液循环槽的出液口(20)、第一反应液进口(21)进入所述物料储罐(102)中；未反应的气体依次经过所述出气口(19)、净化器(6)从气体出口(5)排出；(3) Connect the external high-voltage power supply of the central electrode rod (7), a gas discharge occurs in the space between the central electrode rod (7) and the conductive cylinder (4), nitrogen dioxide and hydrogen are excited to undergo a chemical reaction , to obtain a mixed gas containing nitric oxide; meanwhile, the absorbent in the material storage tank (102) is transported to the slurry distributor (9) through the circulation pump (10) and then along the conductive cylinder (4) The inner wall flows down and collects in the slurry circulation tank (29), and the absorbent that absorbs nitric oxide enters the material storage from the liquid outlet (20) and the first reaction liquid inlet (21) of the slurry circulation tank. In the tank (102); unreacted gas is discharged from the gas outlet (5) through the gas outlet (19) and the purifier (6) successively;
(4)重复步骤(2)、(3)至所述物料储罐(102)吸收剂吸收饱和后，所述物料储罐(102)中吸收饱和的吸收剂从所述第一反应液出口经再生物料泵(11)进入所述再生反应器(103)；(4) Repeat steps (2), (3) until the absorbent in the material storage tank (102) is saturated, and the saturated absorbent in the material storage tank (102) passes through the outlet of the first reaction solution The regeneration material pump (11) enters the regeneration reactor (103);
(5)通过所述加液口(13)向所述再生反应器(103)加入水或盐酸，与所述再生反应器(103)中吸收饱和的吸收剂充分混合获得脱除一氧化氮后的吸收剂，释放出的一氧化氮气体经所述抽气泵(14)与空压机(17)打入的空气混合被氧化为二氧化氮，再通过吸收塔(16)中水或质量分数30％以下的硝酸水溶液吸收，生成高浓度硝酸水溶液，剩余尾气从尾气排出口排出；(5) Add water or hydrochloric acid to the regeneration reactor (103) through the liquid inlet (13), and fully mix with the saturated absorbent in the regeneration reactor (103) to obtain nitric oxide removal The absorbent, the nitrogen monoxide gas that releases is oxidized to nitrogen dioxide through the air mixing of the air pump (14) and the air compressor (17), and then passes through the water or mass fraction in the absorption tower (16) The nitric acid aqueous solution below 30% is absorbed to generate a high concentration nitric acid aqueous solution, and the remaining tail gas is discharged from the tail gas outlet;
(6)加热所述再生反应器(103)对所述脱除一氧化氮后的吸收剂经进行脱水，脱水后的吸收剂从所述第二吸收剂出口通过物料输送泵(12)进入所述物料储罐(102)。(6) heating the regenerative reactor (103) to dehydrate the absorbent after the removal of nitric oxide, and the dehydrated absorbent enters the second absorbent outlet through the material delivery pump (12) The material storage tank (102).
反应过程为：The reaction process is:
N2+O2→2NO (1)N2 +O2 →2NO (1)
FeCl3+NO+H2O→Fe(H2O)(NO)Cl3 (2)FeCl3 +NO+H2 O→Fe(H2 O)(NO)Cl3 (2)
进一步，所述包含氮气和氧气的混合气体配比无特殊要求,一般氧氮体积比控制在1以下，氧气含量少，有利于气体放电，含量10～30％。气流中也可加入氩气、氖气和氦气等惰性气体以增强放电效果，惰性气体在混合气体中的体积百分比一般为1～10％，无特殊要求。Further, there is no special requirement on the ratio of the mixed gas containing nitrogen and oxygen. Generally, the volume ratio of oxygen and nitrogen is controlled below 1, and the oxygen content is small, which is beneficial to gas discharge, and the content is 10-30%. Inert gases such as argon, neon and helium can also be added to the gas flow to enhance the discharge effect. The volume percentage of inert gases in the mixed gas is generally 1-10%, and there is no special requirement.
优选地，所述吸收剂中，氯化铁的质量为水的9倍以上，优选15～25倍，吸收剂在导电筒体表面的形成的液膜厚度一般为1～5mm,可视需要调节。Preferably, in the absorbent, the mass of ferric chloride is more than 9 times that of water, preferably 15 to 25 times, and the thickness of the liquid film formed by the absorbent on the surface of the conductive cylinder is generally 1 to 5 mm, which can be adjusted as needed .
优选地，吸收剂的使用和输送管道一般均保温在50℃～80℃，优选60～80℃，以防吸收剂凝固，所述再生反应器吸收剂脱水时温度一般为65～180℃，优选100～180℃。所述装置中的管路可采用电热带或夹套保温，再生反应器(103)或物料储罐(102)可夹套加热保温。Preferably, the use of the absorbent and the pipeline are generally kept at 50°C to 80°C, preferably 60°C to 80°C, to prevent the absorbent from solidifying. 100～180℃. The pipelines in the device can be insulated with electric heating bands or jackets, and the regenerative reactor (103) or material storage tank (102) can be insulated with jackets.
进一步，本发明所述的气体放电反应吸收器(101)可为圆筒形，筒体为一个电极，筒体中央的轴向中心电极棒为另一电极。反应器上部设置有吸收剂导流装置，使吸收剂沿气体放电反应吸收器(101)的导电筒体(4)内壁流下，在导电筒体(4)内壁形成吸收剂液膜，。所述的反应器类似静电除尘器的结构，电极对也通常有针－板、针－管、线－管和线－板等多种结构组合，效果大体相当。Further, the gas discharge reaction absorber (101) of the present invention can be cylindrical, the cylinder body is one electrode, and the axial central electrode rod in the center of the cylinder body is the other electrode. The upper part of the reactor is provided with an absorbent guide device, so that the absorbent flows down along the inner wall of the conductive cylinder (4) of the gas discharge reaction absorber (101), forming an absorbent liquid film on the inner wall of the conductive cylinder (4). The reactor described above has a structure similar to that of an electrostatic precipitator, and the electrode pairs usually have multiple structural combinations such as needle-plate, needle-tube, line-tube and line-plate, and the effects are generally equivalent.
优选地，电极的供电方式一般为脉冲电源，也可以采用直流(含高频脉冲)和交流电源，效果以采用脉冲电源为好(优选正脉冲电源，峰值电压约30kV，脉冲频率约100Hz，电源功率约50W)，其中供电电压一般为1kV以上，或－1kV以下，优选±10kV～±150kV，正电压和负电压的效果大体相当，正电压稍好一些，脉冲供电的脉冲重复频率一般为1Hz以上，优选10Hz～500Hz，频率增加，输入能量增加，反应转化率提高，脉冲重复频率为500Hz以上时，实际效果提高幅度不大。电极施加电压与电极间距有关，电极间距离越大，施加电压可越高，一般电极距离每增加10mm，电压可增加5kV—10kV，电压高能量释放大，反应转化率高。气体在放电等离子体区的停留时间一般为0.2s以上，停留时间越长，效果越好，优选3s～120s，超过120s，反应转化率提高幅度变小。Preferably, the power supply mode of the electrode is generally a pulse power supply, and direct current (including high-frequency pulse) and alternating current power supply can also be used. The effect is preferably a positive pulse power supply, with a peak voltage of about 30kV and a pulse frequency of about 100Hz. The power is about 50W), and the power supply voltage is generally above 1kV or below -1kV, preferably ±10kV～±150kV. The effect of positive voltage and negative voltage is roughly the same, and the positive voltage is slightly better. The pulse repetition frequency of pulse power supply is generally 1Hz Above, preferably 10 Hz to 500 Hz, the frequency increases, the input energy increases, and the reaction conversion rate increases. When the pulse repetition frequency is above 500 Hz, the actual effect is not greatly improved. The voltage applied to the electrodes is related to the distance between the electrodes. The larger the distance between the electrodes, the higher the applied voltage. Generally, every 10mm increase in the distance between the electrodes, the voltage can be increased by 5kV-10kV. The higher the voltage, the greater the energy release and the higher the conversion rate of the reaction. The residence time of the gas in the discharge plasma region is generally above 0.2s, the longer the residence time, the better the effect, preferably 3s to 120s, and if it exceeds 120s, the increase in the reaction conversion rate becomes smaller.
进一步优选地，所述气体放电反应吸收器(101)内气流温度(反应温度)一般为30～120℃，优选50～90℃，反应器可采用外部加热，也可加热气流后导入所述气体放电反应吸收器(101)。Further preferably, the airflow temperature (reaction temperature) in the gas discharge reaction absorber (101) is generally 30-120°C, preferably 50-90°C, and the reactor can be heated externally, or the airflow can be heated and introduced into the gas Discharge reaction absorber (101).
本发明还提供一种制备一氧化氮的专用装置，所述装置包括依次连接的干燥器(3)、气体放电反应吸收器(101)、物料储罐(102)、物料输送泵(12)、再生反应器(103)、抽气泵(14)与吸收塔(16)；以及控制上述各个部件及管道温度的温控系统；上述各个部件指气体放电反应吸收器(101)、物料储罐(102)、再生反应器(103)、吸收塔(16)；The present invention also provides a special device for preparing nitric oxide, the device includes a dryer (3), a gas discharge reaction absorber (101), a material storage tank (102), a material delivery pump (12), Regenerative reactor (103), air pump (14) and absorption tower (16); and the temperature control system of controlling above-mentioned each parts and pipeline temperature; above-mentioned each parts refer to gas discharge reaction absorber (101), material storage tank (102 ), regeneration reactor (103), absorption tower (16);
所述干燥器(3)设有干燥器进口和干燥器出口，所述干燥器进口通过风机(2)连接气体进口(1)；The drier (3) is provided with a drier inlet and a drier outlet, and the drier inlet is connected to the gas inlet (1) through a fan (2);
所述气体放电反应吸收器(101)包括外接接地电极的导电筒体(4)、设置在所述导电筒体(4)顶端的浆液分布器(9)、贯穿所述浆液分布器(9)的中心电极棒(7)、设于所述导电筒体(10)上部的出气口(19)、设于所述导电筒体(10)底端的浆液循环槽(29)、设于所述浆液循环槽(29)底端的出液口(20)和设于导电筒体(4)上、所述出气口(19)和所述浆液循环槽(29)之间的进气口(18)；所述中心电极棒(7)与外接高压电源连接；所述出气口(19)通过净化器(6)与气体出口(5)连接；The gas discharge reaction absorber (101) includes a conductive cylinder (4) externally connected to a ground electrode, a slurry distributor (9) arranged at the top of the conductive cylinder (4), and a slurry distributor (9) passing through the slurry distributor (9). The center electrode rod (7), the air outlet (19) arranged on the upper part of the conductive cylinder (10), the slurry circulation tank (29) arranged at the bottom of the conductive cylinder (10), the slurry circulation tank (29) arranged on the slurry The liquid outlet (20) at the bottom of the circulation tank (29) and the air inlet (18) arranged on the conductive cylinder (4) between the air outlet (19) and the slurry circulation tank (29); The central electrode rod (7) is connected to an external high-voltage power supply; the gas outlet (19) is connected to the gas outlet (5) through a purifier (6);
所述物料储罐(102)设有注浆口(28)、第一吸收剂进口(22)、第一吸收剂出口(24)、第一反应液进口(21)和第一反应液出口(23)；所述第一反应液进口(22)与所述出液口(20)连接，所述第一吸收剂出口(24)通过循环泵(10)与所述浆液分布器(9)连接；The material storage tank (102) is provided with a grouting port (28), a first absorbent inlet (22), a first absorbent outlet (24), a first reaction liquid inlet (21) and a first reaction liquid outlet ( 23); the first reaction liquid inlet (22) is connected to the liquid outlet (20), and the first absorbent outlet (24) is connected to the slurry distributor (9) through a circulating pump (10) ;
所述再生反应器(103)设有加液口(13)、第二反应液进口(25)、一氧化氮气体出口(26)和第二吸收剂出口(27)；所述第二反应液进口(25)通过再生物料泵(12)与所述第一反应液出口(23)连接，所述第二吸收剂出口(27)通过物料输送泵(12)与所述第一吸收剂进口(22)连接，所述一氧化氮气体出口(26)通过所述抽气泵(14)与所述吸收塔(16)、尾气排出口(15)依次连接；The regenerative reactor (103) is provided with a liquid inlet (13), a second reaction liquid inlet (25), a nitric oxide gas outlet (26) and a second absorbent outlet (27); the second reaction liquid The inlet (25) is connected to the first reaction liquid outlet (23) through the regenerative material pump (12), and the second absorbent outlet (27) is connected to the first absorbent inlet ( 22) connect, and the nitric oxide gas outlet (26) is connected successively with the absorption tower (16) and the tail gas outlet (15) by the air pump (14);
所述抽气泵(14)与所述吸收塔(16)之间的管道上还设有空压机(17)。An air compressor (17) is also provided on the pipeline between the air pump (14) and the absorption tower (16).
于现有技术相比，本发明的有益效果是：采用气体放电和氯化铁吸收剂浆液吸收耦合的方法直接由空气氧化制备硝酸，吸收剂再生后循环利用，大大提高了反应转化率和能源利用率。与传统的工艺相比，工艺简单，运行费用低。Compared with the prior art, the beneficial effect of the present invention is: adopting the coupling method of gas discharge and ferric chloride absorbent slurry absorption to directly prepare nitric acid from air oxidation, and recycle the absorbent after regeneration, greatly improving the reaction conversion rate and energy consumption. utilization rate. Compared with the traditional process, the process is simple and the operating cost is low.
附图说明Description of drawings
图1为所述制备硝酸的装置。Fig. 1 is the described device for preparing nitric acid.
图中：101气体放电反应吸收器；102物料储罐；103再生反应器；1气体进口；2风机；3干燥器；4吸收剂浆液膜；5气体出口；6净化器；7中心电极棒；8绝缘子；9浆液分布器；10循环泵；11再生物料泵；12物料输送泵；13加液口；14抽气泵；15尾气排出口；16吸收塔；17空压机；18进气口；19出气口；20出液口；21第一反应液进口；22第一吸收剂进口；23第一反应液出口；24第一吸收剂出口；25第二反应液进口；26一氧化氮气体出口；27第二吸收剂出口；28注浆口；29浆液循环槽。In the figure: 101 gas discharge reaction absorber; 102 material storage tank; 103 regeneration reactor; 1 gas inlet; 2 fan; 3 dryer; 4 absorbent slurry film; 5 gas outlet; 8 insulator; 9 slurry distributor; 10 circulation pump; 11 recycled material pump; 12 material delivery pump; 13 liquid filling port; 19 Gas outlet; 20 Liquid outlet; 21 First reaction liquid inlet; 22 First absorbent inlet; 23 First reaction liquid outlet; 24 First absorbent outlet; 25 Second reaction liquid inlet; 26 Nitric oxide gas outlet ; 27 second absorbent outlet; 28 grouting port; 29 slurry circulation tank.
具体实施方式Detailed ways
以下结合附图和实施例对本发明作进一步详细描述。The present invention will be described in further detail below in conjunction with the accompanying drawings and embodiments.
下面实施例所用专用装置如下：The special device used in the following examples is as follows:
所述装置包括依次连接的干燥器(3)、气体放电反应吸收器(101)、物料储罐(102)、物料输送泵(12)、再生反应器(103)、抽气泵(14)与吸收塔(16)；以及控制上述各个部件及管道温度的温控系统；上述各个部件指气体放电反应吸收器(101)、物料储罐(102)、再生反应器(103)、吸收塔(16)；The device comprises a dryer (3), a gas discharge reaction absorber (101), a material storage tank (102), a material delivery pump (12), a regenerative reactor (103), an air pump (14) and an absorber connected in sequence. tower (16); and a temperature control system for controlling the above-mentioned components and pipeline temperature; the above-mentioned components refer to gas discharge reaction absorber (101), material storage tank (102), regeneration reactor (103), absorption tower (16) ;
所述干燥器(3)设有干燥器进口和干燥器出口，所述干燥器进口通过风机(2)连接气体进口(1)；The drier (3) is provided with a drier inlet and a drier outlet, and the drier inlet is connected to the gas inlet (1) through a fan (2);
所述气体放电反应吸收器(101)包括外接接地电极的导电筒体(4)、设置在所述导电筒体(4)顶端的浆液分布器(9)、贯穿所述浆液分布器(9)的中心电极棒(7)、设于所述导电筒体(10)上部的出气口(19)、设于所述导电筒体(10)底端的浆液循环槽(29)、设于所述浆液循环槽(29)底端的出液口(20)和设于导电筒体(4)上、所述出气口(19)和所述浆液循环槽(29)之间的进气口(18)；所述中心电极棒(7)与外接高压电源连接；所述出气口(19)通过净化器(6)与气体出口(5)连接；The gas discharge reaction absorber (101) includes a conductive cylinder (4) externally connected to a ground electrode, a slurry distributor (9) arranged at the top of the conductive cylinder (4), and a slurry distributor (9) passing through the slurry distributor (9). The center electrode rod (7), the air outlet (19) arranged on the upper part of the conductive cylinder (10), the slurry circulation tank (29) arranged at the bottom of the conductive cylinder (10), the slurry circulation tank (29) arranged on the slurry The liquid outlet (20) at the bottom of the circulation tank (29) and the air inlet (18) arranged on the conductive cylinder (4) between the air outlet (19) and the slurry circulation tank (29); The central electrode rod (7) is connected to an external high-voltage power supply; the gas outlet (19) is connected to the gas outlet (5) through a purifier (6);
所述物料储罐(102)设有注浆口(28)、第一吸收剂进口(22)、第一吸收剂出口(24)、第一反应液进口(21)和第一反应液出口(23)；所述第一反应液进口(22)与所述出液口(20)连接，所述第一吸收剂出口(24)通过循环泵(10)与所述浆液分布器(9)连接；The material storage tank (102) is provided with a grouting port (28), a first absorbent inlet (22), a first absorbent outlet (24), a first reaction liquid inlet (21) and a first reaction liquid outlet ( 23); the first reaction liquid inlet (22) is connected to the liquid outlet (20), and the first absorbent outlet (24) is connected to the slurry distributor (9) through a circulating pump (10) ;
所述再生反应器(103)设有加液口(13)、第二反应液进口(25)、一氧化氮气体出口(26)和第二吸收剂出口(27)；所述第二反应液进口(25)通过再生物料泵(12)与所述第一反应液出口(23)连接，所述第二吸收剂出口(27)通过物料输送泵(12)与所述第一吸收剂进口(22)连接，所述一氧化氮气体出口(26)通过所述抽气泵(14)与所述吸收塔(16)、尾气排出口(15)依次连接；The regenerative reactor (103) is provided with a liquid inlet (13), a second reaction liquid inlet (25), a nitric oxide gas outlet (26) and a second absorbent outlet (27); the second reaction liquid The inlet (25) is connected to the first reaction liquid outlet (23) through the regenerative material pump (12), and the second absorbent outlet (27) is connected to the first absorbent inlet ( 22) connect, and the nitric oxide gas outlet (26) is connected successively with the absorption tower (16) and the tail gas outlet (15) by the air pump (14);
所述抽气泵(14)与所述吸收塔(16)之间的管道上还设有空压机(17)。An air compressor (17) is also provided on the pipeline between the air pump (14) and the absorption tower (16).
工艺流程：一种制备硝酸的方法的装置是由气体放电反应吸收器(101)、吸收剂循环系统、吸收剂再生系统和相关物料输送管路等辅助系统组成，其中气体放电反应吸收器(101)由中心电极棒(7)和筒体组成，中心电极棒与筒体之间用绝缘子(8)绝缘，筒体上部设置有浆液分布器(9)，吸收剂循环系统主要由物料储罐(102)和循环泵(10)组成，吸收剂浆液通过物料储罐和循环泵输送到所述的浆液分布器，然后沿反应器筒体内壁形成浆液膜(4)流下后返回物料储罐，吸收剂再生系统主要由再生物料泵(11)、再生反应器(103)、抽气泵(14)、空气压缩机(17)和吸收塔(16)组成。其中物料储罐(102)经物料输送泵(11)与设置在气体放电反应吸收器(101)上方的浆液分布器连通(9)，气体放电反应吸收器塔下部与物料储罐(102)连通，物料储罐(102)经再生物料泵(11)与再生反应器(103)连通，再生反应器经物料输送泵(12)与物料储罐连通，再生反应器还与抽气泵(14)、空气压缩机(17)、吸收塔(16)连通，所述的再生反应器(102)还设置有加液口(13)。Process flow: a device for preparing nitric acid is composed of auxiliary systems such as a gas discharge reaction absorber (101), an absorbent circulation system, an absorbent regeneration system and related material delivery pipelines, wherein the gas discharge reaction absorber (101 ) is composed of a central electrode rod (7) and a cylinder. The center electrode rod and the cylinder are insulated by an insulator (8). The upper part of the cylinder is provided with a slurry distributor (9). The absorbent circulation system is mainly composed of a material storage tank ( 102) and a circulation pump (10), the absorbent slurry is transported to the slurry distributor through the material storage tank and the circulation pump, and then returns to the material storage tank after the slurry film (4) flows down along the inner wall of the reactor cylinder to absorb The agent regeneration system is mainly composed of a regeneration material pump (11), a regeneration reactor (103), an air pump (14), an air compressor (17) and an absorption tower (16). Wherein the material storage tank (102) communicates with the slurry distributor (9) arranged above the gas discharge reaction absorber (101) through the material delivery pump (11), and the lower part of the gas discharge reaction absorber tower communicates with the material storage tank (102) , the material storage tank (102) is communicated with the regeneration reactor (103) through the regeneration material pump (11), the regeneration reactor is communicated with the material storage tank through the material delivery pump (12), and the regeneration reactor is also connected with the air pump (14), The air compressor (17) and the absorption tower (16) are connected, and the regeneration reactor (102) is also provided with a liquid inlet (13).
把空气经气体进口(1)、风机(2)和干燥器(3)脱水后导入气体放电反应吸收器(101)，对中心电极棒(7)加上电后，放电棒和筒体之间发生气体放电，气流中的氧气和氮气被激发而发生化学反应，同时把物料储罐(101)中的吸收剂浆液由经物料循环泵(10)输送到反应器筒体上部的浆液分布器(9)后沿反应器筒体内壁流下，吸收反应过程生成的一氧化氮气体，反应后的尾气经过净化器(6)净化后从气体出口(5)排出排放；吸收剂经物料储罐(102)收集后循环使用，吸收饱和后的吸收剂浆液通过再生物料泵(11)输送到再生反应器(103)，然后通过加液口(13)向再生反应器(103)内加入的一定量的水或盐酸溶液与吸收剂物料充分混合，释放出被吸收的一氧化氮气体，并通过抽气泵(14)抽出后经三级吸收塔(16)氧化吸收制备得到硝酸，同时空压机(17)提供一氧化氮氧化所需空气；在再生反应器(103)内脱除被吸收的氮氧化物后的吸收剂浆液经加热和抽气泵抽气脱水，吸收剂再生完毕后，吸收剂浆液经物料输送泵(12)导入物料储罐(102)。The air is dehydrated through the gas inlet (1), the fan (2) and the dryer (3) and then introduced into the gas discharge reaction absorber (101). Gas discharge occurs, oxygen and nitrogen in the gas flow are excited to undergo a chemical reaction, and at the same time, the absorbent slurry in the material storage tank (101) is transported to the slurry distributor ( 9) Then flow down along the inner wall of the reactor cylinder to absorb the nitric oxide gas generated during the reaction process, and the tail gas after the reaction is purified by the purifier (6) and discharged from the gas outlet (5); the absorbent passes through the material storage tank (102 ) is collected and recycled, and the saturated absorbent slurry is transported to the regeneration reactor (103) through the regeneration material pump (11), and then a certain amount of The water or hydrochloric acid solution is fully mixed with the absorbent material to release the absorbed nitric oxide gas, which is taken out by the air pump (14) and then oxidized and absorbed by the three-stage absorption tower (16) to prepare nitric acid. At the same time, the air compressor (17 ) to provide the air needed for the oxidation of nitric oxide; the absorbent slurry after the absorbed nitrogen oxides are removed in the regeneration reactor (103) is dehydrated through heating and suction pump dehydration, and after the regeneration of the absorbent is completed, the absorbent slurry is passed through The material delivery pump (12) is introduced into the material storage tank (102).
实施例1：一种制备硝酸的方法的装置如图1所示。气体放电反应吸收器为直筒形，材料为哈氏合金，反应器高约300mm，内径约为Φ60mm，中心电极棒尺寸为Φ8×300，材质也为合金，中心电极棒与高压电源连接，筒体接地，气体放电区有效长度约150mm。反应器上部设置有吸收浆液分布器导流装置，使所述反应器筒体内壁的接地电极板表面形成均匀吸收剂浆液膜，所述吸收剂由反应器下部的循环槽收集后通过循环泵循环使用。Embodiment 1: a kind of device of the method for preparing nitric acid is as shown in Figure 1. The gas discharge reaction absorber is straight cylindrical, the material is Hastelloy alloy, the height of the reactor is about 300mm, the inner diameter is about Φ60mm, the size of the central electrode rod is Φ8×300, the material is also alloy, the central electrode rod is connected with the high voltage power supply, and the cylinder body Grounded, the effective length of the gas discharge area is about 150mm. The upper part of the reactor is equipped with an absorption slurry distributor flow guide device, so that the surface of the ground electrode plate on the inner wall of the reactor cylinder forms a uniform absorbent slurry film, and the absorbent is collected by the circulation tank at the lower part of the reactor and then circulated through the circulation pump use.
空气流量约为0.5m3/h(含水约0.5％)，反应器内气流温度约75℃，吸收剂含水约6～8％，物料储罐内吸收剂浆液量约10L,循环量约为20L/h。电极供电方式为正脉冲电源，峰值电压约30kV，脉冲频率约100Hz，电源功率约50W。实验结果一氧化氮转化率约为8％，吸收剂对一氧化氮吸收率约95％，连续反应约8小时后吸收剂送再生反应器进行脱吸再生，脱吸时滴加物料重量5％的稀盐酸溶液(浓度为5％)，压缩空气泵流量约为1L/min，经三级吸收制得的硝酸(浓度约为35～40％)。脱吸完毕后的物料再进行抽气脱水，再生反应器温度约120℃，脱水再生约3小时，当物料含水达到约6％时送回物料储罐循环利用。The air flow rate is about 0.5m3 /h (water content is about 0.5%), the air flow temperature in the reactor is about 75°C, the water content of the absorbent is about 6-8%, the absorbent slurry volume in the material storage tank is about 10L, and the circulation volume is about 20L /h. The electrode power supply mode is a positive pulse power supply, the peak voltage is about 30kV, the pulse frequency is about 100Hz, and the power supply is about 50W. Experimental results The conversion rate of nitric oxide is about 8%, and the absorption rate of the absorbent to nitric oxide is about 95%. After continuous reaction for about 8 hours, the absorbent is sent to the regeneration reactor for desorption and regeneration, and 5% of the weight of the material is added dropwise during desorption. The dilute hydrochloric acid solution (concentration is 5%), the compressed air pump flow rate is about 1L/min, and the nitric acid (concentration is about 35-40%) obtained through three-stage absorption. After the desorption is completed, the material is pumped and dehydrated. The temperature of the regeneration reactor is about 120°C, and the dehydration regeneration is about 3 hours. When the water content of the material reaches about 6%, it is sent back to the material storage tank for recycling.
实施例2：在实施例1中空气中加入氩气，分别占总气体为1％和10％，其他条件相同。实验结果一氧化氮转化率分别约为9％和11％。Embodiment 2: In
实施例3：分别以氮氧体积比为9和1代替空气，电极供电方式为直流电源，筒体接地，电压约30kV，电源功率约50W。其他条件和处理过程基本同实施例1。实验结果一氧化氮转化率分别约为6％和4％。Example 3: The nitrogen-oxygen volume ratio is 9 and 1 respectively instead of air, the electrode power supply mode is DC power supply, the cylinder is grounded, the voltage is about 30kV, and the power supply power is about 50W. Other conditions and process are basically the same as in Example 1. Experimental results The nitric oxide conversion rates were about 6% and 4%, respectively.
实施例4：反应器电极供电方式为交流电源(反应器筒体接交流电源另一极)，电压约30kV，频率50Hz，电源功率约50W。其他条件同实施例1。实验结果一氧化氮转化率约为4％。Embodiment 4: The power supply mode of the reactor electrode is an AC power supply (the reactor barrel is connected to the other pole of the AC power supply), the voltage is about 30kV, the frequency is 50Hz, and the power supply power is about 50W. Other conditions are with
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110346065.1ACN114074930B (en) | 2021-03-31 | 2021-03-31 | Method and device for preparing nitric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110346065.1ACN114074930B (en) | 2021-03-31 | 2021-03-31 | Method and device for preparing nitric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114074930A CN114074930A (en) | 2022-02-22 |
| CN114074930Btrue CN114074930B (en) | 2023-03-31 |
Family
ID=80283043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110346065.1AActiveCN114074930B (en) | 2021-03-31 | 2021-03-31 | Method and device for preparing nitric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114074930B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167263B (en)* | 2018-11-13 | 2021-04-13 | 黄华丽 | Nitrogen oxide absorbent slurry and preparation and use methods thereof |
- 2021
- 2021-03-31CNCN202110346065.1Apatent/CN114074930B/enactiveActive
Also Published As
| Publication number | Publication date |
|---|---|
| CN114074930A (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cui et al. | Integrated method of non-thermal plasma combined with catalytical oxidation for simultaneous removal of SO2 and NO | |
| CN100398194C (en) | Dielectric barrier discharge plasma activated carbon in-situ regeneration method and device | |
| CN103736393B (en) | A kind of low temperature plasma removes the method for nitrogen oxide | |
| Cui et al. | An integrated system of dielectric barrier discharge combined with wet electrostatic precipitator for simultaneous removal of NO and SO2: Key factors assessments, products analysis and mechanism | |
| CN112930434B (en) | System and method for purifying engine exhaust ozone | |
| CN207445971U (en) | The complexes of multiple elements design catalytic oxidation treatment industry volatile organic waste gas | |
| CN114074929B (en) | Method and device for preparing nitric oxide | |
| WO2010075751A1 (en) | Method for absorbing and processing of harmful waste gas by electrochemical means | |
| Peng et al. | Study on the mechanism of NO removal by plasma-adsorption catalytic process | |
| CN104961112A (en) | Nitrogen oxide preparation method and device | |
| CN105435603A (en) | Efficient coal-fired flue gas treatment method and device | |
| CN200984495Y (en) | Device for processing waste gas by homogeneous improving of corona discharge by using un-homogeneous catalyst | |
| CN105477986A (en) | Flue gas treatment technology and apparatus thereof | |
| CN106422694A (en) | Method and device for removing sulfur dioxide and nitrogen oxide from airflow | |
| CN107417493B (en) | Method and device for modifying light hydrocarbon absorbed by gas discharge synergistic solution | |
| CN114074930B (en) | Method and device for preparing nitric acid | |
| CN114074948B (en) | Method and device for preparing ammonia | |
| CN115779652A (en) | A method and system for recovering nitrogen oxides from nitrogen oxide tail gas | |
| CN114832838A (en) | Metal/sulfur-persulfate-loaded biochar composite material and preparation and application thereof | |
| CN101785951A (en) | Purification method for organic waste gas | |
| JP2002273161A (en) | Nitrogen oxide decomposition method and apparatus | |
| CN219378979U (en) | Device for removing elemental mercury by electric explosion wire | |
| CN110787626A (en) | A low-temperature plasma-coupled photocatalytic method for oxidizing nitrogen oxides | |
| CN113578000B (en) | Method and device for treating nitrous oxide tail gas by using fuel cell | |
| CN101829485B (en) | Method for desorbing sulfur dioxide in industrial exhaust gas utilizing barometric pressure microwave jet plasma technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |