CN111153439A - Process for producing ferric chloride or polyferric chloride by continuous oxygen oxidation method - Google Patents

Process for producing ferric chloride or polyferric chloride by continuous oxygen oxidation method Download PDF

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CN111153439A
CN111153439A CN202010036159.4A CN202010036159A CN111153439A CN 111153439 A CN111153439 A CN 111153439A CN 202010036159 A CN202010036159 A CN 202010036159A CN 111153439 A CN111153439 A CN 111153439A
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reactor
chloride
ferric chloride
liquid
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吴勇基
蓝立财
丁德才
梁茂杰
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Sriel Environmental Science And Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/10—Halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a process for producing ferric chloride or polyferric chloride by an oxygen oxidation method, which mainly comprises the following steps: hydrochloric acid pickling waste liquid is used as a raw material, waste nitric acid liquid is used as a catalyst, and oxygen is used as an oxidant, and the continuous oxidation is carried out through a multistage reactor to produce ferric chloride or polyferric chloride. The process solves the problems of slow oxidation rate, low intermittent production efficiency and low catalyst recycling rate in the traditional process for producing ferric chloride or polyferric chloride by an oxidation method. The invention improves the traditional production process, thereby improving the oxidation rate, effectively recycling the nitrogen oxide, realizing the continuous production of the ferric chloride or the polyferric chloride, changing waste into valuable and having good environmental and social benefits.

Description

Process for producing ferric chloride or polyferric chloride by continuous oxygen oxidation method
Technical Field
The invention relates to the technical field of compound preparation, in particular to a process for producing ferric chloride or polyferric chloride by continuous oxygen oxidation.
Background
In the steel processing industry, hydrochloric acid solution is generally adopted to clean the surface of steel parts so as to remove oxides on the surface of the steel parts, and a large amount of hydrochloric acid pickling waste liquid is generated in the process. After the stainless steel is acid-washed, nitric acid is needed for passivation treatment, so that a layer of compact oxide film is generated on the surface of the stainless steel, and the surface of the stainless steel has better corrosion resistance, and waste nitric acid liquid is generated. The pickling waste liquid has serious corrosivity, and if the pickling waste liquid is not properly treated, the pickling waste liquid not only pollutes the environment and wastes resources, but also poses threats to the health of human beings. If the waste water is subjected to neutralization and discharge, a large amount of alkali is needed, and high-concentration salt-containing waste water and a large amount of salt-containing sludge are generated; if the roasting method and the reduced pressure concentration method are adopted to recover the acid, the energy consumption is high, the investment is large, the corrosion is serious and the operation environment is poor.
The method for preparing ferric chloride or polyferric chloride mainly adopts a direct oxidation method and a catalytic oxidation method, and has a plurality of patents and documents on the preparation aspect, but the methods have certain disadvantages: the direct oxidation method has too high cost of oxidant, violent reaction process and easy occurrence of potential safety hazard, such as: sodium chlorate oxidation, hydrogen peroxide oxidation, chlorine oxidation; the catalytic oxidation process may emit toxic NOxGas, such as nitrite catalytic oxidation, has the problems of harm to human health and environmental pollution.
The nitrite catalytic oxidation method has the characteristics of low cost, high safety coefficient and the like, and is currently applied to the industrial production of ferric chloride and polyferric chloride. However, the prior art has certain disadvantages: limited gas-liquid contact area, resulting in low oxidation rate; intermittent feeding and discharging are realized, so that the production efficiency is low; the liquid caustic soda has low efficiency of absorbing nitric oxide and strong alkalinity, and the recycling efficiency of nitrogen oxides generated by the catalyst is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a process for producing ferric chloride or polyferric chloride by a continuous oxygen oxidation method, which improves the traditional production process, improves the oxidation rate, effectively recycles nitrogen oxides, realizes the continuous production of the ferric chloride or the polyferric chloride, changes waste into valuable and has good environmental and social benefits.
The process mainly comprises the following steps:
adjusting Fe in hydrochloric acid pickling waste liquid2+% and HCl%, and selecting to add or not add stabilizer as raw material liquid for continuous production; continuously pumping a raw material liquid from the top of the first stage in the multistage reactor, adding a waste nitric acid liquid catalyst from the bottom of the first stage of the multistage reactor, and introducing an oxygen oxidant from the bottom of the last stage of the multistage reactor, so that the system pressure of the multistage reactor is 0.15MPa, and the reaction temperature is 60-80 ℃;
the materials in the reactor pass through a circulating pump from the bottom, one part of the materials is subjected to self circulation, and the other part of the materials is fed into a next-stage reactor; controlling the material flow to ensure that ferrous ions in the material are gradually and completely oxidized through multi-stage reaction, and controlling the mass fraction of the ferrous ions discharged from the last stage reactor to be less than or equal to 0.1%;
nitrogen oxides generated by the reaction are used as catalysts and are used in each stage of reactor through a gas phase balance tube, the residual nitrogen oxide tail gas is firstly absorbed by raw material liquid, and the obtained absorption liquid is reused for production; then the product is absorbed by liquid alkali and used as a catalyst for production;
and aerating and concentrating the discharged material of the reactor to obtain the water treatment agent liquid ferric chloride or the water treatment agent liquid polyferric chloride.
In one embodiment, the feed solution, wherein: when producing ferric chloride products, adjusting Fe in hydrochloric acid pickling waste liquid2+The mass fraction ratio of the percent to the HCl percent is 1.48-1.53: 1, and a stabilizer is not added; adjusting Fe in hydrochloric acid pickling waste liquid during production of poly ferric chloride product2+The mass fraction ratio of the percentage of P to the percentage of HCl is 2.9-15: 1, and a dihydrogen phosphate stabilizer is added to ensure that the mass fraction ratio of the percentage of P to the percentage of Fe in the solution is 0.04: 1.
In one embodiment, the adding amount of the waste nitric acid catalyst is 0.08-0.10% of the mass flow of the raw material liquid calculated by nitrate radical.
In one embodiment, the pressure of the multistage reactor system is 0.15MPa, and oxygen is introduced into the reactor through a pneumatic regulating valve, the pneumatic regulating valve can regulate the opening of the valve according to the set pressure and the actual pressure difference, when the overpressure of the system pressure reaches 0.2MPa, the introduction of oxygen is stopped, and tail gas is discharged from a gas phase balance pipe and is sequentially absorbed by raw material liquid and liquid alkali until the pressure of the system is reduced to 0.15 MPa.
In one embodiment, the reaction temperature of the multistage reactor is 60-80 ℃ by introducing cold water or steam into a jacket of the reactor, so that the reaction temperature of the materials is 60-80 ℃.
In one embodiment, the multistage reactor is a 4-stage reactor, and consists of 1#, 2#, 3#, and 4# reactors, and the oxidation degrees of materials in the 1# to 4# reactors are 25%, 50%, 75%, and 100%, respectively.
In one embodiment, the reactor comprises a reactor body, an ejector, a gas phase balance pipe and a circulating pump; the reactor body is a reaction kettle with a jacket; one port on the right side of the top of the reactor body is communicated with the gas phase balance pipe, and the other port on the right side of the top of the reactor body is connected with a pressure gauge; the middle opening at the top of the reactor body is connected with the lower opening of the ejector, and the right opening of the ejector is communicated with the gas phase balance pipe; the left port at the top of the reactor is connected with the lower port of another ejector, and the right port of the other ejector is connected with the other port at the left side of the top of the reactor; a catalyst or oxygen feeding material is arranged at the left side opening at the bottom of the reactor body; a thermometer is connected with the right port at the bottom of the reactor body; the middle opening at the bottom of the reaction body is connected with a circulating pump, and the other end of the circulating pump is connected with the upper port of the ejector of the current stage or the next stage.
The invention has the advantages that:
1. the hydrochloric acid pickling waste liquid is used as a raw material, the waste nitric acid liquid is used as a catalyst, and the water purifying agent ferric chloride or polyferric chloride is produced, so that the pickling waste liquid is prevented from harming the environment, and the resources are fully utilized. The waste resources are regenerated into the water treatment agent, the production cost is reduced, waste is changed into valuable, and the method has good environmental and social benefits.
2. In the process that materials in the reactor enter the ejector from the bottom of the reactor through the circulating pump and then return to the top of the reactor, the materials form high-speed jet flow through the nozzle of the ejector to cause a partial region vacuum low-pressure state, oxygen and nitrogen oxide gas at the top of the reactor are sucked from the right side port of the ejector and are fully mixed with the materials in the pump, the effective area of gas-liquid mixing is increased, and the oxidation rate of the materials is accelerated. In addition, the gas phase balance pipe is communicated with the top of each stage of reactor, thereby not only balancing the pressure of the system, but also fully utilizing the nitrogen oxides generated by each stage of reaction and effectively reducing the dosage of the catalyst.
3. The tail gas of nitrogen oxide generated in the reaction is absorbed by adopting a raw material solution, and a ferrous iron solution can not only react with nitrogen dioxide, but also react with nitric oxide to form a ferrous nitrogen oxide complex, so that the nitrogen oxide generated in the catalytic oxidation reaction can be effectively absorbed; in order to avoid the pollution of nitrogen oxides to the environment, the nitrogen oxides are absorbed by the raw material liquid and then absorbed by the liquid alkali, and the raw material liquid and the liquid alkali after absorbing the nitrogen oxides are both recycled for production, so that the use amount of the catalyst in the production process is reduced.
4. The process realizes continuous industrial production of feeding and discharging at the same time, avoids a production mode of intermittent feeding and discharging, maximizes the utilization rate of equipment, and greatly improves the production efficiency. The process has the advantages of high efficiency, easily controlled production process and operation.
5. The process can be used for producing the ferric chloride of the water treatment agent and the polyferric chloride, does not generate waste resources in the reaction process, and can be used for sewage treatment.
Drawings
FIG. 1 is a flow chart of the process steps for producing ferric chloride or polyferric chloride by continuous oxygen oxidation according to one embodiment of the present invention
FIG. 2 is a schematic diagram of a four-stage reactor.
Wherein: 1, feeding raw materials; 2, an ejector; 3. 5, a liquid phase interface at the top of the reactor; 4. 6, a gas phase interface at the top of the reactor; 7 gas phase balance tube; 8 a reactor body; 9 feeding a catalyst; 10 reactor jacket steam inlet; 11 a reactor jacket cooling water outlet; 12 a reactor jacket steam condensate outlet; 13 a reactor jacket cooling water inlet; 14 reactor bottom outlet; 15 circulating pump; 16 oxygen feed; 17 gas phase balance tube tail gas outlet; 18 discharging the finished product; 19 reactor jacket.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
To further illustrate a process for producing ferric chloride or poly-ferric chloride by a continuous oxygen oxidation method, an embodiment of the present invention is shown in fig. 1 by combining a schematic structural diagram of a reactor in fig. 2, and the process for producing ferric chloride or poly-ferric chloride by a continuous oxygen oxidation method mainly comprises the following steps:
step S110, adjusting Fe in the hydrochloric acid pickling waste liquid2+% and HCl%, optionally adding stabilizer, and continuously producing raw material liquid.
In the present embodiment, when producing an iron chloride product, Fe in the hydrochloric acid pickling waste liquid is adjusted2+The mass fraction ratio of the percent to the HCl percent is 1.48-1.53: 1, and a stabilizer is not added; if producing poly ferric chloride product, adjusting Fe in hydrochloric acid pickling waste liquor2+The mass fraction ratio of the percentage of P to the percentage of HCl is 2.9-15: 1, and a dihydrogen phosphate stabilizer is added to ensure that the mass fraction ratio of the percentage of P to the percentage of Fe in the solution is 0.04: 1. In the process of preparing the product by the oxygen oxidation method, divalent iron ions and hydrogen chloride just completely react, namely the obtained product has no divalent iron ions and free acid, and Fe in the raw material liquid at the moment2+The mass fraction ratio of the percent to the HCl percent is 1.53: 1. Free acid with a certain concentration is required in the ferric chloride product, the mass fraction of the free acid in the ferric chloride liquid is less than or equal to 0.40 percent in the national standard water treatment agent ferric chloride (GB-T4482-2018), otherwise, the ferric chloride product is easy to generate turbidity and is not beneficial to normal use. Before the production process, the mass fraction of free acid in the ferric chloride product is required to be 0-0.4%, so that the product performance and quality are ensured, and therefore, the hydrochloric acid is added in the raw material blending processFe in pickling solution2+The mass fraction ratio of the percent to the HCl percent is 1.48-1.53: 1. In hydrochloric acid pickling solution, the concentration of ferrous ions is high, the concentration of hydrogen chloride is low, and Fe is common2+The mass fraction ratio of the percent to the HCl percent is more than 1.53:1, and hydrochloric acid solution can be adopted for blending; alternatively, the composition may be formulated with a hydrochloric acid solution containing ferric ions or ferrous ions. The ferric chloride product is produced without adding a stabilizer, and the ferric chloride with a certain concentration of free acid can exist stably. In the process of producing the poly-ferric chloride, a certain amount of stabilizing agent needs to be introduced, and the shelf life of the poly-ferric chloride is directly influenced due to the poor stability of the poly-ferric chloride and the addition of less or no stabilizing agent. In the process of producing the polyferric chloride, the process adopts the dihydric phosphate, and the stability of the ferric chloride is enhanced and the storage time is prolonged by changing the hydrolysis structure of ferric ions. The adding amount of the dihydric phosphate is that the mass fraction ratio of P percent to Fe percent is 0.04:1, and the produced polyferric chloride product not only can obtain better flocculation capacity, but also can be stored for at least 2 years. Similarly, the production of poly-ferric chloride products by oxygen oxidation method also needs to pass Fe in raw material liquid2+The mass fraction ratio of% to HCl% ensures that the mass fraction of the salinity in the poly-ferric chloride product meets the mass fraction of the salinity in the water treatment agent poly-ferric chloride (HG/T4672-2014) of the industry standard of 5-30%. Therefore, the hydrochloric acid pickling waste liquid is used as a raw material, oxygen is oxidized to produce the poly ferric chloride, and Fe in the raw material liquid is adjusted2+The mass fraction ratio of the percent to the HCl percent is 2.9-15: 1. Adjusting Fe in hydrochloric acid pickling waste liquid2+% and HCl% by weight, ferrous chloride solid or solution, other hydrochloric acid pickling waste liquid, hydrochloric acid solution, etc.
And step S120, continuously pumping the raw material liquid from the top of the primary reactor, adding the waste nitric acid liquid catalyst from the bottom of the primary reactor, adding the oxygen oxidant from the bottom of the secondary reactor, and controlling the system pressure of the reactor to be 0.15MPa and the reaction temperature to be 60-80 ℃.
In one embodiment, the waste nitric acid catalyst and the oxygen oxidant enter the reactor in a countercurrent mode, and the catalyst enters the first-stage reactor, mainly the content of ferrous ions in materials in the first-stage reactor is the highest, the oxidation degree of the materials is the lowest, and the ferrous ions are quickly oxidized into ferric ions by adding the catalyst; in addition, the method also avoids the over-high nitrogen oxide in the last stage of the reactor and even in the product, which is not beneficial to the full utilization of the catalyst, and simultaneously reduces the using amount of the catalyst. The adding amount (calculated by nitrate radical) of the waste nitric acid catalyst is 0.08-0.10% of the mass flow of the raw material liquid.
Oxygen is continuously introduced into the reactor through a pneumatic regulating valve, the raw material liquid gradually consumes the oxygen in the oxidation process, the oxygen consumption is gradually reduced along with the increase of the oxidation degree of the material, the pressure of the system is gradually increased, and the consumed oxygen is rapidly supplemented when the pressure of the system is less than 0.15 MPa; when the system pressure reaches 0.15MPa, the oxygen regulating valve can regulate the opening of the valve according to the system pressure, so that the pressure of the reaction system is kept at 0.15 MPa; meanwhile, a protective pressure of 0.2MPa is set as a control point for cutting off the introduction of oxygen and the exhaust emission, so that the potential safety hazard caused by overhigh pressure due to the failure of a reaction system is avoided. After the tail gas is discharged, the tail gas is sequentially absorbed by the raw material liquid and the liquid caustic soda until the pressure of the system is reduced to 0.15 MPa. The discharged nitrogen oxides in the tail gas are firstly subjected to complexing reaction on nitric oxide by utilizing ferrous iron ions to form a ferrous nitrogen oxide complex, so that the nitric oxide in the tail gas can be effectively reduced, nitrogen dioxide is dissolved in a solution to form dilute nitric acid, the ferrous iron ions can also be oxidized, the ferrous iron ions can effectively absorb the nitrogen oxides, the absorption liquid can be used in production, and the adding amount of a catalyst in the production can also be reduced; meanwhile, the liquid caustic soda is added for supplement and absorption, so that the pollution to the atmosphere and the harm to the health of human beings are avoided.
The reaction temperature is controlled by introducing steam or cooling water into the jacket for heat exchange, so that the reaction temperature is 60-80 ℃. For example: the reaction speed in the reactor is too fast, the temperature rises too fast, the reaction temperature is higher than 80 ℃, certain risks exist for the service life and the safety of equipment, cooling water is introduced into a jacket of the reactor to cool the reactor, the temperature of the cooling water rises after heat exchange, and the obtained water after heat exchange can be used for preheating a raw material liquid or heating other materials. The reaction system is provided with a pressure system and a temperature control system, so that the reaction speed is further improved, and the progress of the reaction is better monitored.
S130, circulating the materials in the reactor from the bottom by a circulating pump, wherein one part of the materials is circulated by the circulating pump, and the other part of the materials is fed into a next-stage reactor; controlling the material flow to ensure that ferrous ions in the material are gradually and completely oxidized through multi-stage reaction, and controlling the mass fraction of the ferrous ions discharged from the last-stage reactor to be less than or equal to 0.1 percent.
In this embodiment, the mixing process of the material in the reactor with oxygen and nitrogen oxides is completed by the interaction of the circulating pump and the ejector. The materials in the reactor are pumped into the ejector through the circulating pump, and the ejector forms vacuum low pressure through high-speed jet flow of the nozzle to extract oxygen or nitrogen oxide at the top of the reactor, so that the oxygen or nitrogen oxide is fully mixed, the contact area of gas-liquid reaction is increased, and the oxidation reaction is accelerated. After the material is sprayed, one part of the material is forced to circulate in the reactor of the material, and the other part of the material enters the next-stage reactor for reaction until the mass fraction of ferrous ions in the last-stage reactor is less than or equal to 0.1 percent. The oxidation degree of the materials in the multistage reactor is in a certain gradient by controlling the circulation flow of the materials and the supply flow of the materials supplied to the next stage. Such as: in a four-stage reactor system, the oxidation degree of materials in each reactor is respectively 25%, 50%, 75% and 100%. For another example: a sampling port is arranged between the reactor and the circulating pump, the current oxidation degree is judged by detecting the mass fraction of ferrous ions in each stage of reactor, and then the flow of the materials is regulated and controlled to meet the requirement of the oxidation degree.
And step S140, nitrogen oxides generated by the reaction are used as catalysts and are used in each stage of reactor through a gas phase balance tube, and the residual nitrogen oxide tail gas is firstly absorbed by raw material liquid and then absorbed by liquid caustic soda, and is circularly used for production.
In the present embodiment, each reactor generates oxidation-reduction reaction, which generates nitrogen oxide gas, and the nitrogen oxide gas is collected at the top of the reactor, and in order to make the catalyst fully utilized and maintain the pressure of the equilibrium system, a gas phase equilibrium tube is arranged to be respectively communicated with the top of each reactor, so that nitrogen oxide generated by the reaction can be supplied to each stage of reactor for catalytic oxidation reaction. For another example, in the step S120, the system pressure is controlled to be 0.15MPa, when the system pressure reaches 0.2MPa, the entry of oxygen is cut off, the gas phase equilibrium tube opens the tail gas emission regulating valve, and the discharged nitrogen oxide tail gas is absorbed by the ferrous iron raw material liquid and sodium hydroxide and is reused for production.
In one embodiment, the material flow is further described with reference to FIG. 2. The prepared raw material liquid enters an ejector 2 through a raw material feeding 1, and nitrogen oxide generated by reaction enters the ejector from a gas phase interface 4 at the top of a reactor body 8 and is mixed with the raw material liquid to enter a liquid phase interface 3 at the top of the reactor; the material enters a circulating pump 15 from a discharge hole 14 at the bottom of the reactor, the circulating pump pumps a part of the material into another ejector, one interface of the other ejector is communicated with a gas phase balance pipe 7, and the material, the nitrogen oxide and the oxygen are fully mixed in the ejector and enter a liquid phase interface 5 at the top of the reactor; the other part of the materials enter an ejector through a circulating pump and are transferred into a next-stage reactor, and the processes are sequentially carried out until the mass fraction of ferrous ions discharged from the bottom of a fourth-stage reactor is less than or equal to 0.1%; catalyst feed 9 enters the reaction system from the bottom of the first stage reactor, while oxygen feed 16 enters the reaction system from the bottom of the fourth stage reactor.
And S150, aerating and concentrating the discharged material of the reactor to obtain the water treatment agent liquid ferric chloride meeting the national standard or the water treatment agent liquid polyferric chloride meeting the industrial standard.
In the embodiment, a small amount of nitrogen oxides in the finished product solution prepared by the oxygen catalytic oxidation method enter a finished product intermediate tank, compressed air or oxygen is used for stripping, and the generated nitrogen oxides are absorbed by ferrous ions and liquid caustic soda and then are reused for production. The blow-stripped polyferric chloride can meet the iron (Fe) in the water treatment agent polyferric chloride 2014 (HG/T4672-3+) Mass fraction is more than or equal to 8 percent, ferrous iron (Fe)2+) Not more than 0.2 percent, 5 to 30 percent of basicity mass fraction and not more than 0.3 percent of water-insoluble substance mass fraction. For another example: evaporating and concentrating the ferric chloride to ensure that the ferric chloride (Fe) is not concentrated enough after stripping3+) Mass fraction is more than or equal to 14 percent, ferrous iron (Fe)2+) Not more than 0.1 percent, free acid (calculated by HCl) not more than 0.4 percent, insoluble substancesThe mass fraction is less than or equal to 0.5 percent, so that the iron chloride water treatment agent meets the national standard of iron chloride water treatment (GB-T4482-2018).
The following continues to give specific examples:
example 1
Adjusting Fe in hydrochloric acid pickling waste liquid2+% by mass of HCl% to obtain a ferric chloride raw material solution (Fe: 10.08%, Fe)2+：9.97％，HCl：6.58％，Fe2+Percent: HCl% ═ 1.51:1), the feedstock was transferred to reactor # 1 through an ejector at a flow rate of 14.5 tons/hr, and nitric acid (NO) was used3 -10.01%) at 120 kg/h (NO)3 -And the mass ratio of the oxygen to the raw material liquid is 0.08%), oxygen is introduced from the bottom of the No. 1 reactor, the system pressure is kept at 0.15MPa, the material temperature is controlled to be 70 ℃, and the discharge from the bottom of the No. 4 reactor is qualified (Fe: 9.85% of Fe2+: 0.01%, HCl: 0.12%), the finished product enters a finished product intermediate tank, is blown off by air for 2 hours, and then is transferred to an evaporator for evaporation and concentration to obtain a ferric chloride product (Fe: 14.18% of Fe2+: 0.01%, HCl: 0.17 percent) of the total weight of the powder meets the national standard of water treatment agent ferric chloride (GB-T4482-2018).
Example 2
Adjusting Fe in hydrochloric acid pickling waste liquid2+% by mass of sodium dihydrogen phosphate stabilizer and HCl%, to obtain a poly (ferric chloride) raw material solution (Fe: 13.75%, Fe)2+：12.62％，HCl：4.30％，P％/Fe％＝0.04，Fe2+Percent: HCl percent is 2.94:1), the raw material liquid is transferred into a No. 1 reactor through an ejector at the flow rate of 16 tons/hour, and nitric acid liquid (NO) is wasted3 -10.25%) at 130 kg/h (NO)3 -And the mass ratio of the oxygen to the raw material liquid is 0.08%), oxygen is introduced from the bottom of the No. 1 reactor, the system pressure is kept at 0.15MPa, the material temperature is controlled to be 75 ℃, and the discharge from the bottom of the No. 4 reactor is qualified (Fe: 13.12% of Fe2+: 0.01%, B: 5.71%), the finished product enters a finished product intermediate tank, and the finished product is blown off for 2 hours by air, so that the product meets the industrial standard of water treatment agent poly-ferric chloride (HG/T4672-2014).
Example 3
Adjustment ofFe in hydrochloric acid pickling waste liquid2+% by mass of HCl% to obtain a ferric chloride raw material solution (Fe: 10.60%, Fe)2+：10.21％，HCl：6.85％，Fe2+Percent: HCl percent is 1.49:1), the raw material liquid is transferred into a No. 1 reactor through an ejector at the flow rate of 15.3 tons/hour, and nitric acid liquid (NO) is wasted3 -11.65%) at 120 kg/h (NO)3 -And the mass ratio of the oxygen to the raw material liquid is 0.09%), the oxygen enters from the bottom of the No. 1 reactor, the oxygen enters from the bottom of the No. 4 reactor, the system pressure is kept at 0.15MPa, the material temperature is controlled to be 75 ℃, and the discharge from the bottom of the No. 4 reactor is qualified (Fe: 10.37% of Fe2+: 0.01%, HCl: 0.23%), the finished product enters a finished product intermediate tank, is blown off by air for 2 hours, and then is transferred to an evaporator for evaporation and concentration to obtain a ferric chloride product (Fe: 14.05%, Fe2+: 0.01%, HCl: 0.32 percent) of the total weight of the iron chloride-based water treatment agent meets the national standard of water treatment agent iron chloride (GB-T4482-2018).
Example 4
Adjusting Fe in hydrochloric acid pickling waste liquid2+% by mass of sodium dihydrogen phosphate stabilizer and HCl%, to obtain a poly (ferric chloride) raw material solution (Fe: 11.21%, Fe)2+：11.14％，HCl：1.74％，P％/Fe％＝0.04，Fe2+Percent: HCl% ═ 6.40:1), the feedstock was transferred to reactor # 1 through an ejector at a flow rate of 16.5 tons/hr, and nitric acid (NO) was used3 -13.25%) at 130 kg/h (NO)3 -And the mass ratio of the oxygen to the raw material liquid is 0.10%), oxygen is introduced from the bottom of the No. 1 reactor, the system pressure is kept at 0.15MPa, the material temperature is controlled to be 75 ℃, and the discharge from the bottom of the No. 4 reactor is qualified (Fe: 10.77%, Fe2+: 0.01%, B: 11.44%), the finished product enters a finished product intermediate tank, and the finished product is blown off for 2 hours by air, so that the product meets the industrial standard of water treatment agent poly-ferric chloride (HG/T4672-2014).
Various other changes and modifications to the above embodiments and concepts will become apparent to those skilled in the art, and all such changes and modifications are intended to be included within the scope of the present invention as defined in the appended claims.

Claims (7)

1. A process for producing ferric chloride or polyferric chloride by a continuous oxygen oxidation method is characterized by comprising the following steps:
A. adjusting Fe in hydrochloric acid pickling waste liquid2+% and HCl%, and selecting to add or not to add a stabilizer as a raw material liquid for continuous production; continuously pumping a raw material liquid from the top of the first stage in the multistage reactor, adding a waste nitric acid liquid catalyst from the bottom of the first stage of the multistage reactor, and introducing an oxygen oxidant from the bottom of the last stage of the multistage reactor, so that the system pressure of the multistage reactor is 0.15MPa, and the reaction temperature is 60-80 ℃;
B. the materials in the reactor pass through a circulating pump from the bottom, one part of the materials is subjected to self circulation, and the other part of the materials is fed into a next-stage reactor; controlling the material flow to ensure that ferrous ions in the material are gradually and completely oxidized through multi-stage reaction, and controlling the mass fraction of the ferrous ions discharged from the last stage reactor to be less than or equal to 0.1%;
C. nitrogen oxides generated by the reaction are used as catalysts and are used in each stage of reactor through a gas phase balance tube, the residual nitrogen oxide tail gas is firstly absorbed by raw material liquid, and the obtained absorption liquid is reused for production; then the product is absorbed by liquid alkali and used as a catalyst for production;
D. and aerating and concentrating the discharged material of the reactor to obtain the water treatment agent liquid ferric chloride or the water treatment agent liquid polyferric chloride.
2. The process for producing ferric chloride or polyferric chloride by a continuous oxygen oxidation process as claimed in claim 1, wherein the feed solution, wherein: when producing ferric chloride products, adjusting Fe in hydrochloric acid pickling waste liquid2+The mass fraction ratio of the percent to the HCl percent is 1.48-1.53: 1, and a stabilizer is not added; adjusting Fe in hydrochloric acid pickling waste liquid during production of poly ferric chloride product2+The mass fraction ratio of the percentage of P to the percentage of HCl is 2.9-15: 1, and a dihydrogen phosphate stabilizer is added to ensure that the mass fraction ratio of the percentage of P to the percentage of Fe in the solution is 0.04: 1.
3. The process for producing ferric chloride or polyferric chloride by using the continuous oxygen oxidation method as claimed in claim 1, wherein the addition amount of the waste nitric acid catalyst is 0.08-0.10% of the mass flow of the raw material liquid calculated by nitrate radical.
4. The process for producing ferric chloride or polyferric chloride by using a continuous oxygen oxidation method as claimed in claim 1, wherein the pressure of the multistage reactor system is 0.15MPa, in a specific embodiment, oxygen is introduced into the reactor through a pneumatic regulating valve, the opening of the valve is adjusted by the pneumatic regulating valve according to the set pressure and the actual pressure difference, when the system pressure is over-pressurized to 0.2MPa, the introduction of oxygen is stopped, and tail gas is discharged from the gas phase balance pipe and sequentially absorbed by the raw material liquid and the liquid caustic soda until the system pressure is reduced to 0.15 MPa.
5. The process for producing ferric chloride or polyferric chloride by using the continuous oxygen oxidation method as claimed in claim 1, wherein the specific implementation manner of the multistage reactor with the reaction temperature of 60-80 ℃ is that cold water or steam is introduced into a jacket of the reactor, so that the material reaction temperature is 60-80 ℃.
6. The process for producing ferric chloride or polyferric chloride by using the continuous oxygen oxidation method as claimed in claim 1, wherein the multistage reactor is a 4-stage reactor, and is composed of 1#, 2#, 3#, and 4# reactors, and the oxidation degree of materials in the 1# to 4# reactors is 25%, 50%, 75%, and 100%, respectively.
7. The process for producing ferric chloride or polyferric chloride by a continuous oxygen oxidation process as claimed in any one of claims 1 to 6, wherein the reactor comprises a reactor body, an ejector, a gas phase equilibrium tube, a circulation pump; the reactor body is a reaction kettle with a jacket; one port on the right side of the top of the reactor body is communicated with the gas phase balance pipe, and the other port on the right side of the top of the reactor body is connected with a pressure gauge; the middle opening at the top of the reactor body is connected with the lower opening of the ejector, and the right opening of the ejector is communicated with the gas phase balance pipe; the left port at the top of the reactor is connected with the lower port of another ejector, and the right port of the other ejector is connected with the other port at the left side of the top of the reactor; a catalyst or oxygen feeding material is arranged at the left side opening at the bottom of the reactor body; a thermometer is connected with the right port at the bottom of the reactor body; the middle opening at the bottom of the reaction body is connected with a circulating pump, and the other end of the circulating pump is connected with the upper port of the ejector of the current stage or the next stage.
CN202010036159.4A 2020-01-14 2020-01-14 Process for producing ferric chloride or polyferric chloride by continuous oxygen oxidation method Pending CN111153439A (en)

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