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WO2013181827A1 - Method and device for producing plant nitrogen fertilizer nutritive solution with seawater as raw material - Google Patents

Method and device for producing plant nitrogen fertilizer nutritive solution with seawater as raw material Download PDF

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Publication number
WO2013181827A1
WO2013181827A1 PCT/CN2012/076595 CN2012076595W WO2013181827A1 WO 2013181827 A1 WO2013181827 A1 WO 2013181827A1 CN 2012076595 W CN2012076595 W CN 2012076595W WO 2013181827 A1 WO2013181827 A1 WO 2013181827A1
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Prior art keywords
seawater
ammonia
nitrogen fertilizer
raw material
carbon dioxide
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PCT/CN2012/076595
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French (fr)
Chinese (zh)
Inventor
葛文宇
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Ge Wenyu
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Priority to PCT/CN2012/076595 priority Critical patent/WO2013181827A1/en
Publication of WO2013181827A1 publication Critical patent/WO2013181827A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D9/00—Nitrates of sodium, potassium or alkali metals in general
    • C01D9/08—Preparation by double decomposition
    • C01D9/10—Preparation by double decomposition with ammonium nitrate
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C5/00—Fertilisers containing other nitrates
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00—Fertilisers characterised by their form
    • C05G5/20—Liquid fertilisers
    • C05G5/23—Solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/103—Water
    • B01D2252/1035—Sea water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the invention relates to a method for processing seawater, in particular to a zero-emission, ring-shaped mirror A method and a device for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material.
  • seawater 71% of the Earth's surface area It is the ocean, and seawater is the largest material resource on earth, so humans have begun to use seawater very early.
  • the various elements in seawater are mostly present in seawater in the form of salt compounds.
  • the salt content in seawater varies from region to region in the world (each region has accurate data), such as seawater near the equator.
  • the highest amount of salt About 4%, the sea salt in the sea near the estuary of the great rivers on the land is only about 3%.
  • the world-famous famous chemist Dimar Dittmar A survey report on 'substances in seawater' has been published. Since then, countries have adopted the standard listed in the following table in engineering applications.
  • the standard seawater practical salinity value published by the International Association of Ocean Physics (IAPSO) is also 35000PPM (3.5%).
  • seawater One of the most important characteristics of seawater is that the ratio of the various salts contained in seawater is approximately constant regardless of the salt concentration, so these main elements in seawater are also called 'conservative elements'.
  • the salt chemical industry which extracts various salt products from seawater or elemental materials in seawater
  • the desalination industry that is, from seawater. Extracting fresh water
  • the biggest disadvantage of the above two types of industries is that the remaining seawater after production is discharged back to the sea.
  • the present invention is to solve the above technical problems existing in the prior art, and provides a zero emission and a ring mirror.
  • the technical solution of the present invention is: A method for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material, which is characterized by the following steps:
  • a Taking seawater as a raw material, adding ammonia gas and carbon dioxide gas to the seawater to fully mix the salt compounds in the seawater with ammonia and carbon dioxide to form Ammonia-carbon composite water, the amount of ammonia added is 0.45 to 0.55 of the mass of the salt compound in seawater; and the amount of the carbon dioxide argon gas is 0.7 to 0.75 of the mass of the salt compound in seawater. ;
  • ammonium nitrate to the ammonia carbon composite water and mix the two thoroughly.
  • the ammonium nitrate is added in an amount of 0.56 of the mass of the salt compound in seawater. ⁇ 0.65, a nitrogen fertilizer nutrient solution.
  • the invention relates to a method for producing a plant nitrogen fertilizer nutrient solution by using seawater as a raw material, which is provided with a vertical tower, and two vertical drain plates are built in the vertical tower, and the top of the vertical tower is a seawater inlet, and is located at the upper and lower sides.
  • the vertical tower in the middle of the leakage plate is provided with an ammonia gas inlet and a carbon dioxide gas inlet, and the bottom end of the vertical tower is connected to the beginning of the horizontal reaction tank through a pipeline, and is also provided at the beginning of the horizontal reaction tank.
  • the present invention is a nitrogen fertilizer nutrient solution required to chemically modify the salty seawater, the largest resource on the earth, into a plant (the nitrogen fertilizer concentration is 10%). Left and right), does not produce surplus seawater, eliminates pollution emissions and benefits human society.
  • the invention can also use the remaining concentrated brine produced by the 'seawater desalination' industry as a raw material, and the nitrogen fertilizer concentration contained in the obtained nitrogen fertilizer nutrient solution can reach 20%. Left and right, it solves the problem of pollution discharge in the 'seawater desalination' industry, while reducing the production cost of desalination and increasing production efficiency.
  • FIG. 1 is a schematic structural view of an embodiment of the present invention.
  • a Taking seawater as a raw material, adding ammonia gas and carbon dioxide gas to the seawater to fully mix the salt compounds in the seawater with ammonia and carbon dioxide to form Ammonia-carbon composite water, the amount of ammonia added is 0.45 to 0.55 of the mass of the salt compound in seawater; and the amount of the carbon dioxide gas is 0.7 to 0.75 of the mass of the salt compound in seawater. ;
  • ammonium nitrate to the ammonia carbon composite water and mix the two thoroughly.
  • the ammonium nitrate is added in an amount of 0.56 of the mass of the salt compound in seawater. ⁇ 0.65, a nitrogen fertilizer nutrient solution.
  • FIG. 1 it can be realized by the device shown in FIG. 1 , which is provided with a vertical tower 1 , and two vertical drain plates with a leak hole on the upper and lower towers are built in the vertical tower 1 2
  • the top of the vertical tower 1 is a seawater inlet 3, and an ammonia inlet 4 and a carbon dioxide gas inlet 5 are disposed on a vertical tower 1 located between the upper and lower drain plates 2, and the vertical tower 1
  • the bottom end of the horizontal reaction tank 7 is connected to the beginning of the horizontal reaction tank 7, and a stirrer 8 and an ammonium nitrate inlet 9 are provided at the beginning of the horizontal reaction tank 7, and the end of the horizontal reaction tank 7 is provided.
  • Nitrogen nutrient solution outlet 10 in the middle of the horizontal reaction tank 7 there are three staggered baffles 11 , horizontal reactor 7
  • the first mixing chamber, the second reaction chamber, the third reaction chamber and the fourth reaction chamber are separated.
  • Entrance 4 and carbon dioxide gas inlet 5 enter vertical tower 1 When the gas rises, it is squeezed upward from the leak hole of the upper drain plate, and forms a gas and liquid exchange with the seawater, which generates a lot of bubble foam, so that the ammonia gas and the carbon dioxide gas are thoroughly mixed with the various salts in the seawater, and the reaction is incomplete.
  • the reaction is continued at the lower drain plate, so that the salt in the seawater is converted into nitrogen fertilizer after being combined with ammonia and carbon dioxide: ammonium chloride, ammonium sulfate, ammonium bromide; part of the modification becomes carbonate : sodium bicarbonate, magnesium carbonate, calcium carbonate, potassium carbonate; forming a new 'ammonia-carbon composite water';
  • the 'ammonia-carbon composite water' produced by the first step reaction enters the beginning of the horizontal reaction tank 7 through the line 6 (the first mixing chamber), and the ammonium nitrate is Ammonium nitrate inlet 9 Entering horizontal reaction tank 7 through agitator 8
  • the 'ammonia-carbon composite water' is thoroughly mixed with ammonium nitrate, and enters the second reaction chamber through the baffle plate with the hole in the middle, and then enters the third reaction chamber from the lower side of the second reaction chamber partition, and then from the third reaction chamber.
  • the separator enters the fourth reaction chamber, and after repeated mixing reactions, all the carbonates formed in the first step of the reaction are reacted with ammonium nitrate to form a new nitrogen fertilizer.
  • the method can also be used to chemically modify the remaining concentrated brine produced by the 'seawater desalination' industry, and the nitrogen concentration in the obtained product can reach about 20%.
  • the first step of the reaction to produce fertilizer is:
  • the second step of the reaction to produce fertilizer is:
  • Potassium nitrate KNO 3 ammonium carbonate ( NH 4 ) 2 CO 3 ; ammonium hydrogencarbonate NH 4 HCO 3 ;
  • 50% of the total mass of the nitrogen fertilizer in the solution and 20% of the total mass of the nitrogen fertilizer can be added.
  • Potassium ore powder, the fineness of the ore powder should reach 200 mesh or more, and the nitrogen fertilizer nutrient solution can be turned into a compound nutrient solution.
  • the phosphate rock powder will be slowly converted into monocalcium phosphate in the soil and then absorbed by the plant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Agronomy & Crop Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)

Abstract

The present invention relates to a method and a device for producing plant nitrogen fertilizer nutritive solution with seawater as raw material. The method comprises the following steps: a. taking seawater as raw material, adding ammonia (the amount is 0.45-0.55, based on the weight of salt compounds in seawater) and CO2 (the amount is 0.7-0.75, based on the weight of salt compounds in seawater) gas to the seawater for mixing salt compounds in seawater with ammonia and CO2 completely, and obtaining ammonia carbonate composite water; b. adding ammonium nitrate (the amount is 0.56-0.65, based on the weight of salt compounds in seawater) to the composite water, mixing them completely, and obtaining nitrogen fertilizer nutritive solution.

Description

以海水为原料生产植物氮肥营养液的方法及设备  Method and device for producing plant nitrogen fertilizer nutrient solution by using seawater as raw material
技术领域： Technical field:
本发明涉及一种加工利用海水的方法，尤其是一种零排放、利于环镜的 以海水为原料生产植物氮肥营养液的方法及设备。 The invention relates to a method for processing seawater, in particular to a zero-emission, ring-shaped mirror A method and a device for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material.
背景技术： Background technique:
地球的表面积中 71% 是海洋，海水是地球上最大的物质资源，因此人类很早就开始利用海水。海水中各种元素大都是以盐类化合物的形式存在于海水中，全世界各大洋各个不同地区的海水中含盐量也有区别（每个地区均有准确检测数据），如赤道附近的海水含盐量最高可达 4% 左右，陸地的大江大河入海口附近海域的海水含盐量只有 3% 左右。 1872 年，世界公认著名化学家狄马尔 Dittmar 所公开了'海水中所含物质'的捡测报告，此后各国在工程应用中都採用下表所列这个标准，国际海洋物理协会（ IAPSO ）所公开的标准的海水实用盐度值亦为 35000PPM （ 3.5% ）。 71% of the Earth's surface area It is the ocean, and seawater is the largest material resource on earth, so humans have begun to use seawater very early. The various elements in seawater are mostly present in seawater in the form of salt compounds. The salt content in seawater varies from region to region in the world (each region has accurate data), such as seawater near the equator. The highest amount of salt About 4%, the sea salt in the sea near the estuary of the great rivers on the land is only about 3%. In 1872, the world-famous famous chemist Dimar Dittmar A survey report on 'substances in seawater' has been published. Since then, countries have adopted the standard listed in the following table in engineering applications. The standard seawater practical salinity value published by the International Association of Ocean Physics (IAPSO) is also 35000PPM (3.5%).
序号 Serial number 物质 substance 化学符号 chemical symbol PPM PPM 总固体中 % % of total solids 备注 Remarks
1 1 氯化钠 Sodium chloride NaCl NaCl 27213 27213 77.76 77.76
2 2 氯化镁 Magnesium chloride MgCl2 MgCl 2 3807 3807 10.88 10.88
3 3 硫酸镁 Magnesium sulfate MgSO4 MgSO 4 1658 1658 4.73 4.73
4 4 硫酸钙 Calcium sulfate CaSO4 CaSO 4 1260 1260 3.60 3.60
5 5 硫酸钾 Potassium sulfate K2SO4 K 2 SO 4 863 863 2.46 2.46
6 6 碳酸钙 Calcium carbonate CaCO3 CaCO 3 123 123 0.35 0.35
7 7 溴化镁 Magnesium bromide MgBr2 MgBr 2 76 76 0.22 0.22
总计 total 35000ppM 35000ppM 100.00% 100.00%
海水有个最大特点是：不论含盐浓度如何，海水中所含有的各种盐之间比值关系近似恒定，所以海水中的这些主要元素又被称为'保守元素'。目前，应用海水做生产原料的行业有二大类：一类是盐化工产业，是从海水中提取各种盐类产品或海水中的元素物质；另一类是海水淡化产业，即从海水中提取淡水；上述两类产业最大的缺点是将生产后的剩余海水又排放回大海。由于剩余海水成分不全，改变了近海水域海水中各种成分的含量，造成海洋生物死亡或变迁，最终会导致类似渤海湾这类半封闭海湾变成死海。迄今为止，始终无法彻底解决这一世界性的难题。 One of the most important characteristics of seawater is that the ratio of the various salts contained in seawater is approximately constant regardless of the salt concentration, so these main elements in seawater are also called 'conservative elements'. At present, there are two major types of industries that use seawater to produce raw materials: one is the salt chemical industry, which extracts various salt products from seawater or elemental materials in seawater; the other is the desalination industry, that is, from seawater. Extracting fresh water; the biggest disadvantage of the above two types of industries is that the remaining seawater after production is discharged back to the sea. Due to the incomplete composition of the remaining seawater, the content of various components in the seawater in the offshore waters has been changed, resulting in the death or change of marine life, which will eventually lead to a semi-closed bay like the Bohai Bay becoming a Dead Sea. So far, this worldwide problem has not been completely solved.
发明内容： Summary of the invention:
本发明是为了解决现有技术所存在的上述技术问题，提供一种 零排放、利于环镜的 以海水为原料生产植物氮肥营养液的方法及设备。 The present invention is to solve the above technical problems existing in the prior art, and provides a zero emission and a ring mirror. A method and a device for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material.
本发明的技术解决方案是： 一种以海水为原料生产植物氮肥营养液的方法，其特征在于按如下步骤进行： The technical solution of the present invention is: A method for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material, which is characterized by the following steps:
a. 取海水为原料，向海水中加入氨气及二氧化碳气体，使海水中的盐类化合物与氨及二氧化碳充分混合，生成 氨碳复合水，所述 氨气的加入量为海水中盐类化合物质量的 0.45 ～ 0.55 ；所述二氧化碳氩气体的加入量为 海水中盐类化合物质量的 0.7 ～ 0.75 ； a. Taking seawater as a raw material, adding ammonia gas and carbon dioxide gas to the seawater to fully mix the salt compounds in the seawater with ammonia and carbon dioxide to form Ammonia-carbon composite water, the amount of ammonia added is 0.45 to 0.55 of the mass of the salt compound in seawater; and the amount of the carbon dioxide argon gas is 0.7 to 0.75 of the mass of the salt compound in seawater. ;
b. 向 氨碳复合水中加入硝酸铵并使两者充分混合，所述硝酸铵的加入量 为海水中盐类化合物质量的 0.56 ～ 0.65 ，生成氮肥营养液。 b. Add ammonium nitrate to the ammonia carbon composite water and mix the two thoroughly. The ammonium nitrate is added in an amount of 0.56 of the mass of the salt compound in seawater. ~ 0.65, a nitrogen fertilizer nutrient solution.
一种上述以海水为原料生产植物氮肥营养液的方法用设备，设有竖直塔，在竖直塔内置有上下两层漏板，所述竖直塔的顶端为海水入口，在位于上下两层漏板中间的竖直塔上设有氨气入口及二氧化碳气体入口，所述竖直塔的底端通过管路与卧式反应罐的始端相接，在卧式反应罐的始端处还设有搅拌器及 硝酸铵入口，在 卧式反应罐的终端处设有 液氮肥营养液出口，在 卧式反应罐的中部有多个交错设置的挡流隔板。 The invention relates to a method for producing a plant nitrogen fertilizer nutrient solution by using seawater as a raw material, which is provided with a vertical tower, and two vertical drain plates are built in the vertical tower, and the top of the vertical tower is a seawater inlet, and is located at the upper and lower sides. The vertical tower in the middle of the leakage plate is provided with an ammonia gas inlet and a carbon dioxide gas inlet, and the bottom end of the vertical tower is connected to the beginning of the horizontal reaction tank through a pipeline, and is also provided at the beginning of the horizontal reaction tank. There is a stirrer and At the inlet of the ammonium nitrate, there is a liquid nitrogen nutrient solution outlet at the end of the horizontal reaction tank, and a plurality of staggered baffles are arranged in the middle of the horizontal reaction tank.
本 发明是将地球上的最大资源-苦涩的咸海水经过化学改性后变成植物所需要的氮肥营养液（氮肥浓度为 10% 左右），不产生剩余海水，消除了污染排放，造福于人类社会。应用本发明也可以'海水淡化'行业所产生的剩余的浓盐水为原料，所得氮肥营养液中所含的氮肥浓度可达 20% 左右，即解决了'海水淡化'行业的污染排放问题，同时降低了海水淡化生产成本，提高的生产效益。 The present invention is a nitrogen fertilizer nutrient solution required to chemically modify the salty seawater, the largest resource on the earth, into a plant (the nitrogen fertilizer concentration is 10%). Left and right), does not produce surplus seawater, eliminates pollution emissions and benefits human society. The invention can also use the remaining concentrated brine produced by the 'seawater desalination' industry as a raw material, and the nitrogen fertilizer concentration contained in the obtained nitrogen fertilizer nutrient solution can reach 20%. Left and right, it solves the problem of pollution discharge in the 'seawater desalination' industry, while reducing the production cost of desalination and increasing production efficiency.
附图说明： BRIEF DESCRIPTION OF THE DRAWINGS:
图 1 是本发明实施例的结构示意图。 1 is a schematic structural view of an embodiment of the present invention.
具体实施方式： detailed description:
下面将结合附图说明本发明的具体实施方式。 Specific embodiments of the present invention will be described below with reference to the accompanying drawings.
本发明的具体实施方式是按如下步骤进行： The specific embodiment of the present invention is carried out as follows:
a. 取海水为原料，向海水中加入氨气及二氧化碳气体，使海水中的盐类化合物与氨及二氧化碳充分混合，生成 氨碳复合水，所述 氨气的加入量为海水中盐类化合物质量的 0.45 ～ 0.55 ；所述二氧化碳气体的加入量为 海水中盐类化合物质量的 0.7 ～ 0.75 ； a. Taking seawater as a raw material, adding ammonia gas and carbon dioxide gas to the seawater to fully mix the salt compounds in the seawater with ammonia and carbon dioxide to form Ammonia-carbon composite water, the amount of ammonia added is 0.45 to 0.55 of the mass of the salt compound in seawater; and the amount of the carbon dioxide gas is 0.7 to 0.75 of the mass of the salt compound in seawater. ;
b. 向 氨碳复合水中加入硝酸铵并使两者充分混合，所述硝酸铵的加入量 为海水中盐类化合物质量的 0.56 ～ 0.65 ，生成氮肥营养液。 b. Add ammonium nitrate to the ammonia carbon composite water and mix the two thoroughly. The ammonium nitrate is added in an amount of 0.56 of the mass of the salt compound in seawater. ~ 0.65, a nitrogen fertilizer nutrient solution.
具体可用如 1 所示设备实现，设有竖直塔 1 ，在竖直塔 1 内置有上下具有漏孔的两层漏板 2 ，所述竖直塔 1 的顶端为海水入口 3 ，在位于上下两层漏板 2 中间的竖直塔 1 上设有氨气入口 4 及二氧化碳气体入口 5 ，所述竖直塔 1 的底端通过管路 6 与卧式反应罐 7 的始端相接，在卧式反应罐 7 的始端处还设有搅拌器 8 及 硝酸铵入口 9 ，在 卧式反应罐 7 的终端处设有 氮肥营养液出口 10 ，在 卧式反应罐 7 的中部有三个交错设置的挡流隔板 11 ，将卧式反应罐 7 分出第一混合仓、第二反应仓、第三反应仓及第四反应仓。 Specifically, it can be realized by the device shown in FIG. 1 , which is provided with a vertical tower 1 , and two vertical drain plates with a leak hole on the upper and lower towers are built in the vertical tower 1 2 The top of the vertical tower 1 is a seawater inlet 3, and an ammonia inlet 4 and a carbon dioxide gas inlet 5 are disposed on a vertical tower 1 located between the upper and lower drain plates 2, and the vertical tower 1 The bottom end of the horizontal reaction tank 7 is connected to the beginning of the horizontal reaction tank 7, and a stirrer 8 and an ammonium nitrate inlet 9 are provided at the beginning of the horizontal reaction tank 7, and the end of the horizontal reaction tank 7 is provided. Nitrogen nutrient solution outlet 10 , in the middle of the horizontal reaction tank 7 there are three staggered baffles 11 , horizontal reactor 7 The first mixing chamber, the second reaction chamber, the third reaction chamber and the fourth reaction chamber are separated.
具体操作过程如下： The specific operation process is as follows:
  1. a. 将海水从 海水入口 3 处注入竖直塔 1 ，氨气、二氧化碳气体分别从氨气  a. Inject seawater from the seawater inlet 3 into the vertical tower 1 , ammonia and carbon dioxide gas respectively from ammonia
入口 4 及二氧化碳气体入口 5 进入竖直塔 1 ， 气体上升就从上层漏板的漏孔向上挤，与海水形成气、液交流，产生很多气泡泡沫，使氨气和二氧化碳气体与海水中的各种盐充分混合、反应；反应不完全的会在下层漏板处继续反应，这样海水中的盐经过与氨和二氧化碳的化合反应后，一部分改性变成为氮肥：氯化铵、硫酸铵、溴化铵；一部分改性变成为碳酸盐：碳酸氢钠、碳酸镁、碳酸钙、碳酸钾；形成新'氨碳复合水'； Entrance 4 and carbon dioxide gas inlet 5 enter vertical tower 1 When the gas rises, it is squeezed upward from the leak hole of the upper drain plate, and forms a gas and liquid exchange with the seawater, which generates a lot of bubble foam, so that the ammonia gas and the carbon dioxide gas are thoroughly mixed with the various salts in the seawater, and the reaction is incomplete. The reaction is continued at the lower drain plate, so that the salt in the seawater is converted into nitrogen fertilizer after being combined with ammonia and carbon dioxide: ammonium chloride, ammonium sulfate, ammonium bromide; part of the modification becomes carbonate : sodium bicarbonate, magnesium carbonate, calcium carbonate, potassium carbonate; forming a new 'ammonia-carbon composite water';
反应方程式如下： The reaction equation is as follows:
氯化钠 NaCl+ 氨 NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 碳酸氢钠 NaHCO 3 + 氯化铵 NH 4 Cl ；Sodium chloride NaCl + ammonia NH 3 + carbon dioxide CO 2 + water H 2 O → sodium hydrogencarbonate NaHCO 3 + ammonium chloride NH 4 Cl ;
氯化镁 MgCl2+ 氨 2NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 氯化铵 2NH 4 C+ 碳酸镁 MgCO 3 Magnesium chloride MgCl 2 + ammonia 2NH 3 + carbon dioxide CO 2 + water H 2 O → ammonium chloride 2NH 4 C+ magnesium carbonate MgCO 3
硫酸镁 MgSO4+ 氨 2NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 碳酸镁 MgCO 3 + 硫酸铵 (NH 4 ) 2 SO 4 Magnesium sulfate MgSO 4 + ammonia 2NH 3 + carbon dioxide CO 2 + water H 2 O → magnesium carbonate MgCO 3 + ammonium sulfate (NH 4 ) 2 SO 4
硫酸钙 CaSO 4 + 氨 2NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 碳酸钙 CaCO 3 + 硫酸铵 (NH 4 )2SO 4 Calcium sulfate CaSO 4 + ammonia 2NH 3 + carbon dioxide CO 2 + water H 2 O → calcium carbonate CaCO 3 + ammonium sulfate (NH 4 ) 2 SO 4
硫酸钾 K2SO4+ 氨 2NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 硫酸铵 (NH4)2SO4+ 碳酸钾 K 2 CO 3 Potassium sulfate K 2 SO 4 + ammonia 2NH 3 + carbon dioxide CO 2 + water H 2 O → ammonium sulfate (NH 4 ) 2 SO 4 + potassium carbonate K 2 CO 3
溴化镁 MgBr 2 + 氨 2NH 3 + 二氧化碳 CO 2 + 水 H 2 O → 溴化铵 2NH 4 Br+ 碳酸镁 MgCO 3 Magnesium bromide MgBr 2 + ammonia 2NH 3 + carbon dioxide CO 2 + water H 2 O → ammonium bromide 2NH 4 Br+ magnesium carbonate MgCO 3
b. 第一步反应生成的'氨碳复合水'通过管路 6 进入卧式反应罐 7 的始端（第一混合仓）内，硝酸铵从 硝酸铵入口 9 进入 卧式反应罐 7 ，通过搅拌器 8 使'氨碳复合水'与硝酸铵充分混合，经过在中间设孔的挡流隔板进入第二反应仓、再从第二反应仓隔板下面进入第三反应仓、再从第三反应仓隔板上面进入第四反应仓，经过反复混合反应，将所有在第一步化合反应中所形成的碳酸盐全都与硝酸铵反应改性成为新的氮肥。 b. The 'ammonia-carbon composite water' produced by the first step reaction enters the beginning of the horizontal reaction tank 7 through the line 6 (the first mixing chamber), and the ammonium nitrate is Ammonium nitrate inlet 9 Entering horizontal reaction tank 7 through agitator 8 The 'ammonia-carbon composite water' is thoroughly mixed with ammonium nitrate, and enters the second reaction chamber through the baffle plate with the hole in the middle, and then enters the third reaction chamber from the lower side of the second reaction chamber partition, and then from the third reaction chamber. The separator enters the fourth reaction chamber, and after repeated mixing reactions, all the carbonates formed in the first step of the reaction are reacted with ammonium nitrate to form a new nitrogen fertilizer.
反应方程式如下： The reaction equation is as follows:
碳酸氢钠 NaHCO 3 + 硝酸铵 NH 4 NO 3 → 硝酸钠 NaNO 3 + 碳酸氢铵 NH 4 HCO 3 ； Sodium bicarbonate NaHCO 3 + ammonium nitrate NH 4 NO 3 → sodium nitrate NaNO 3 + ammonium bicarbonate NH 4 HCO 3 ;
碳酸镁 MgCO 3 + 硝酸铵 2NH 4 NO 3 → 硝酸镁 Mg(NO 3 ) 2 + 碳酸铵 (NH 4 ) 2 CO 3 Magnesium carbonate MgCO 3 + Ammonium nitrate 2NH 4 NO 3 → Magnesium nitrate Mg(NO 3 ) 2 + Ammonium carbonate (NH 4 ) 2 CO 3
碳酸钙 CaCO 3 + 硝酸铵 2NH 4 NO 3 → 硝酸钙 Ca(NO 3 ) 2 + 碳酸铵 (NH 4 ) 2 CO 3 Calcium carbonate CaCO 3 + Ammonium nitrate 2NH 4 NO 3 → Calcium nitrate Ca(NO 3 ) 2 + Ammonium carbonate (NH 4 ) 2 CO 3
碳酸钾 K 2 CO 3 + 硝酸铵 2NH 4 NO 3 → 硝酸钾 2KNO 3 + 碳酸铵 (NH 4 ) 2 CO 3 Potassium carbonate K 2 CO 3 + Ammonium nitrate 2NH 4 NO 3 → Potassium nitrate 2KNO 3 + Ammonium carbonate (NH 4 ) 2 CO 3
即经过二次复合反应后海水中的全部盐就都变成为氮肥，产物中所含的氮肥浓度为 10% 左右。应用本方法也可对'海水淡化'行业所产生的剩余的浓盐水进行化学改性，所得的产物中的氮肥浓度就可达 20% 左右。 That is, after the secondary recombination reaction, all the salts in the seawater become nitrogen fertilizer, and the nitrogen concentration in the product is 10%. Left and right. The method can also be used to chemically modify the remaining concentrated brine produced by the 'seawater desalination' industry, and the nitrogen concentration in the obtained product can reach about 20%.
第一步反应生成化肥有： The first step of the reaction to produce fertilizer is:
氯化铵 NH 4 Cl 、硫酸铵 (NH 4 ) 2 SO 4 、 溴化铵 NH 4 Br Ammonium chloride NH 4 Cl , ammonium sulfate (NH 4 ) 2 SO 4 , ammonium bromide NH 4 Br
第二步反应生成化肥有： The second step of the reaction to produce fertilizer is:
硝酸钠 NaNO 3 ；硝酸镁 Mg(NO 3 ) 2 ；硝酸钙 Ca(NO 3 ) 2 ； Sodium nitrate NaNO 3 ; magnesium nitrate Mg ( NO 3 ) 2 ; calcium nitrate Ca ( NO 3 ) 2 ;
硝酸钾 KNO 3 ；碳酸铵 (NH 4 ) 2 CO 3 ；碳酸氢铵 NH 4 HCO 3 ； Potassium nitrate KNO 3 ; ammonium carbonate ( NH 4 ) 2 CO 3 ; ammonium hydrogencarbonate NH 4 HCO 3 ;
可以在第二步卧式反应罐中再添加些相当于溶液中氮肥总质量的 50% 磷矿粉和氮肥总质量的 20% 钾矿粉，矿粉的细度要达到 200 目以上，就可以使氮肥营养液变成复合营养液，其中磷矿石粉会在土壤中缓慢转变成磷酸一钙后被植物所吸收。 In the second step of the horizontal reaction tank, 50% of the total mass of the nitrogen fertilizer in the solution and 20% of the total mass of the nitrogen fertilizer can be added. Potassium ore powder, the fineness of the ore powder should reach 200 mesh or more, and the nitrogen fertilizer nutrient solution can be turned into a compound nutrient solution. The phosphate rock powder will be slowly converted into monocalcium phosphate in the soil and then absorbed by the plant.

Claims (2)

  1. 一种以海水为原料生产植物氮肥营养液的方法，其特征在于按如下步骤进行： A method for producing plant nitrogen fertilizer nutrient solution using seawater as a raw material, which is characterized by the following steps:
    a. 取海水为原料，向海水中加入氨气及二氧化碳气体，使海水中的盐类化合物与氨及二氧化碳充分混合，生成 氨碳复合水，所述 氨气的加入量为海水中盐类化合物质量的 0.45 ～ 0.55 ；所述二氧化碳气体的加入量为 海水中盐类化合物质量的 0.7 ～ 0.75 ；a. taking seawater as a raw material, adding ammonia gas and carbon dioxide gas to the seawater, and thoroughly mixing the salt compound in the seawater with ammonia and carbon dioxide to form ammonia carbon composite water, The amount of ammonia added is 0.45 to 0.55 of the mass of the salt compound in seawater; the amount of carbon dioxide added is 0.7 to 0.75 of the mass of the salt compound in seawater. ;
    b. 向 氨碳复合水中加入硝酸铵并使两者充分混合，所述硝酸铵的加入量 为海水中盐类化合物质量的 0.56 ～ 0.65 ，生成氮肥营养液。b. Add ammonium nitrate to the ammonia carbon composite water and mix the two thoroughly. The ammonium nitrate is added in an amount of 0.56 to 0.65 of the mass of the salt compound in seawater. , the production of nitrogen fertilizer nutrient solution.
  2. 一种如权利要求 1 所述以海水为原料生产植物氮肥营养液的方法用设备，其特征在于：设有竖直塔（ 1 ），在竖直塔（ 1 ）内置有上下两层漏板（ 2 ），所述竖直塔（ 1 ）的顶端为海水入口（ 3 ），在位于上下两层漏板（ 2 ）中间的竖直塔（ 1 ）上设有氨气入口（ 4 ）及二氧化碳气体入口（ 5 ），所述竖直塔（ 1 ）的底端通过管路（ 6 ）与卧式反应罐（ 7 ）的始端相接，在卧式反应罐（ 7 ）的始端处还设有搅拌器（ 8 ）及硝酸铵入口（ 9 ），在 卧式反应罐（ 7 ）的终端处设有 氮肥营养液出口（ 10 ），在卧式反应罐（ 7 ）的中部有多个交错设置的挡流隔板（ 11 ）。A method for producing a plant nitrogen fertilizer nutrient solution using seawater as a raw material according to claim 1, characterized in that a vertical tower (1) is provided in the vertical tower (1) There are two upper and lower leakage plates (2) built in, the top of the vertical tower (1) is a seawater inlet (3), and is arranged on a vertical tower (1) located between the upper and lower two leakage plates (2) Ammonia inlet ( 4 And a carbon dioxide gas inlet (5), the bottom end of the vertical tower (1) is connected to the beginning of the horizontal reaction tank (7) through a line (6) at the beginning of the horizontal reaction tank (7) Also equipped with a blender ( 8 And the ammonium nitrate inlet (9), at the end of the horizontal reaction tank (7) is provided with a nitrogen nutrient solution outlet (10), and in the middle of the horizontal reaction tank (7) there are a plurality of staggered baffles (11 ).
PCT/CN2012/076595 2012-06-07 2012-06-07 Method and device for producing plant nitrogen fertilizer nutritive solution with seawater as raw material WO2013181827A1 (en)

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WO2010103729A1 (en) * 2009-03-11 2010-09-16 株式会社 東芝 Method and system for removing carbon dioxide from exhaust gas by utilizing seawater
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CN102153113A (en) * 2011-03-01 2011-08-17 中国中轻国际工程有限公司 Process for producing mirabilite type bittern, sodium carbonate, sodium chloride, sodium sulfate and ammonium chloride

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Publication number Priority date Publication date Assignee Title
CN87100251A (en) * 1987-01-10 1987-07-29 陈鹏 Production of sodium nitrate
CN1455757A (en) * 2000-06-16 2003-11-12 保罗·龙韦德 seawater desalination method
WO2008110405A2 (en) * 2007-03-15 2008-09-18 Silicon Fire Ag Method and device for binding gaseous co2 and for treating flue gases with sodium carbonate compounds
WO2010103729A1 (en) * 2009-03-11 2010-09-16 株式会社 東芝 Method and system for removing carbon dioxide from exhaust gas by utilizing seawater
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Publication number Priority date Publication date Assignee Title
CN108883364A (en) * 2016-01-21 2018-11-23 方尾私人有限公司 The method and apparatus of carbon dioxide are removed from flue gas

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