CN116216904A - Method for treating iron-containing waste hydrochloric acid without catalytic oxidation - Google Patents

Method for treating iron-containing waste hydrochloric acid without catalytic oxidation Download PDF

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Publication number
CN116216904A
CN116216904A CN202211697523.7A CN202211697523A CN116216904A CN 116216904 A CN116216904 A CN 116216904A CN 202211697523 A CN202211697523 A CN 202211697523A CN 116216904 A CN116216904 A CN 116216904A
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China
Prior art keywords
iron
hydrochloric acid
waste hydrochloric
oxidation
reaction
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Pending
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CN202211697523.7A
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Chinese (zh)
Inventor
蒋银峰
许世侠
王桂玉
惠天翔
张珂
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Jiangsu Yongbao Environmental Protection Technology Co ltd
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Jiangsu Yongbao Environmental Protection Technology Co ltd
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Priority to CN202211697523.7A priority Critical patent/CN116216904A/en
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    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/02—Temperature
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/03—Pressure

Abstract

The invention discloses a method for treating iron-containing waste hydrochloric acid without catalytic oxidation, and relates to the technical field of wastewater treatment. From the atomic reaction point of view, the invention realizes the catalytic oxidation-free treatment of the iron-containing waste hydrochloric acid by controlling the reaction temperature and the reaction pressure to obtain an iron chloride solution product, and further adjusts the iron content and the acidity in the iron-containing waste hydrochloric acid and the addition amount of oxygen, so that ferrous ions in the iron-containing waste hydrochloric acid can be more fully oxidized. The whole process of the method is energy-saving and environment-friendly, only oxygen is needed to be added for oxidation, and no tail gas pollution is generated. The method for treating the waste hydrochloric acid containing iron by catalytic oxidation-free method of the invention aims at Fe 2+ High oxidation efficiency of Fe 2+ The conversion rate of the catalyst is not less than 95 percent, and the utilization rate of raw materials is high.

Description

Method for treating iron-containing waste hydrochloric acid without catalytic oxidation
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for treating iron-containing waste hydrochloric acid without catalytic oxidation.
Background
In the steel processing process, a hydrochloric acid pickling process is generally used, ferric chloride solution is generally prepared from iron-containing waste hydrochloric acid generated by pickling through an oxidation reaction, the current common oxidation mode is catalytic oxidation, nitric acid or nitrite is mostly adopted as a catalyst in the catalytic oxidation process, and oxygen is combined for catalytic oxidation, but the oxidation mode has the problems of raw material resource waste or environmental hazard, such as toxic gas of nitrogen oxides generated after the oxidation reaction, and environmental pollution is caused.
The prior art discloses a process for producing ferric chloride or poly ferric chloride by a continuous oxygen oxidation method, which utilizes waste nitric acid liquid as a catalyst and combines oxygen to catalyze and oxidize ferrous ions in hydrochloric acid pickling waste liquid, and meanwhile, part of ferrous ions are used for absorbing nitrogen oxide tail gas to generate ferrous nitrogen oxide complex, so that the pollution of nitrogen oxide to the environment is prevented, but the part of ferrous ions used for absorbing the tail gas cannot participate in oxidation reaction to produce ferric iron, so that the recycling rate of the ferric ions is low, the whole production process is complex, and the energy consumption is larger.
Disclosure of Invention
The invention aims to overcome the defects and defects of low iron ion recycling rate and tail gas pollution existing in the conventional catalytic oxidation treatment of iron-containing waste hydrochloric acid by utilizing a nitric acid and oxygen system, and provides a method for treating the iron-containing waste hydrochloric acid without catalytic oxidation.
The above object of the present invention is achieved by the following technical scheme:
a method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
introducing oxygen into waste hydrochloric acid containing iron to perform oxidation reaction to obtain ferric chloride solution; the reaction temperature is 150-200 ℃, and the reaction pressure is 1-3 kPa; no catalyst or oxidation auxiliary agent is added in the reaction process.
The following are to be described:
the invention aims at the atomic reaction of Fe in the waste hydrochloric acid containing Fe 2+ Oxygen of (2)Thermodynamic calculation is carried out on the heat of the chemical reaction to obtain the temperature and pressure conditions required by the heat of the chemical reaction of the corresponding oxidation reaction, thereby controlling Fe in the waste hydrochloric acid containing iron 2+ The oxidation reaction temperature and pressure realize the oxidation of waste hydrochloric acid containing iron under the condition of no need of catalyst, and the ferric chloride solution is obtained.
In addition, the oxygen introduced into the iron-containing waste hydrochloric acid is continuously consumed, and the whole reaction pressure is not influenced.
Specifically, the iron content in the iron-containing waste hydrochloric acid is Fe 2 O 3 5 to 30%, for example, 5%, 10%, 13%, 15%, 17%, 20%, 30%; the iron content is mass content.
Preferably, the iron content in the iron-containing waste hydrochloric acid is Fe 2 O 3 The content is 10-20%.
The iron content in the iron-containing waste hydrochloric acid can influence the temperature and the pressure in the oxidation reaction process, and the temperature and the pressure in the catalytic oxidation reaction process can be better controlled by adjusting the range of the iron content in the iron-containing waste hydrochloric acid, so that the catalytic oxidation reaction can be smoothly carried out.
More preferably, the iron content in the iron-containing waste hydrochloric acid is Fe 2 O 3 13 to 17%, more preferably 15%.
Specifically, the acidity of the iron-containing waste hydrochloric acid is 5-10%.
Acidity of waste hydrochloric acid containing iron as H + Concentration meter, the acidity can also influence the temperature and pressure of oxidation reaction, and Fe 2+ H is consumed in the oxidation process + Thus, control of acidity is advantageous in improving oxidation efficiency.
Preferably, the acidity of the iron-containing spent hydrochloric acid is 6.5 to 8.5%, more preferably 7%.
The iron content and acidity of the iron-containing spent hydrochloric acid also affects the Fe in the final ferric chloride solution 3+ The content and HCl content can be controlled simultaneously to obtain Fe 3+ Ferric chloride solution with higher content and lower HCl content.
Specifically, the addition amount of the oxygen is 1-5% of the mass addition amount of the iron-containing waste hydrochloric acid.
More specifically, the oxygen is added in an amount of 1 to 3% by mass, preferably 2% by mass, of the iron-containing waste hydrochloric acid.
The addition amount of oxygen is required to meet the oxidation requirement of ferrous iron in the iron-containing waste hydrochloric acid of the reaction system, and when the mass addition amount of oxygen is 1-3%, the oxidation efficiency is better when the iron ions in the iron-containing waste hydrochloric acid are oxidized.
Preferably, the reaction temperature is 165 to 185 ℃, more preferably 180 ℃.
Preferably, the reaction pressure is 1.5 to 2.5kPa, more preferably 2kPa.
Preferably, the oxidation reaction is carried out with stirring.
The specific stirring speed may be selected according to conventional conditions required for uniform mixing of the raw materials, for example, a speed of 1000rpm.
Specifically, the ferric chloride solution after the oxidation reaction is used for preheating the iron-containing waste hydrochloric acid raw material.
And preheating the waste hydrochloric acid raw material liquid containing iron by the ferric chloride solution obtained after the oxidation reaction through a multi-process heat exchanger, so that the preheating utilization is realized, and the energy consumption in the production process is reduced.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a method for treating iron-containing waste hydrochloric acid without catalytic oxidation, which is characterized in that from the atomic reaction perspective, the iron-containing waste hydrochloric acid without catalytic oxidation is obtained by controlling the reaction temperature and the reaction pressure, and then the iron content and the acidity in the iron-containing waste hydrochloric acid and the addition amount of oxygen are further regulated, so that ferrous ions in the iron-containing waste hydrochloric acid can be more fully oxidized. The whole process of the method is energy-saving and environment-friendly, only oxygen is needed to be added for oxidation, and no tail gas pollution is generated.
The method for treating the waste hydrochloric acid containing iron by catalytic oxidation-free method of the invention aims at Fe 2+ High oxidation efficiency of Fe 2+ The conversion rate of the catalyst is not less than 95 percent, and the utilization rate of raw materials is high.
Detailed Description
Fe in the iron-containing waste hydrochloric acid 2 O 3 The content is measured by potassium dichromate titration, and the acidity is measured by acid-base neutralization titration.
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 15% of content and 7% of acidity), stirring is started, the rotating speed is 1000rpm, the temperature of the reaction kettle is set to be 180 ℃, the working pressure is 2.0kPa, 0.6g of oxygen is pumped (namely, the mass addition amount is 2%), and the ferric chloride solution product is obtained after full oxidation.
Example 2
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 10% of content and 5% of acidity), stirring at 1000rpm, setting the temperature of a reaction kettle at 150 ℃, setting the working pressure at 3.0kPa, pumping 0.3g of oxygen (i.e. the mass addition amount is 1%), and fully oxidizing to obtain an iron chloride solution product.
Example 3
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 13% of content and 6.5% of acidity), stirring is started, the rotating speed is 1000rpm, the temperature of the reaction kettle is set at 165 ℃, the working pressure is 2.5kPa, 0.6g of oxygen is pumped (namely, the mass addition amount is 2%), and the ferric chloride solution product is obtained after full oxidation.
Example 4
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 17% of content, 8.5% of acidity), turning on stirring at 1000rpm, setting the temperature of a reaction kettle at 185 ℃, setting the working pressure at 1.5kPa, pumping 0.9g of oxygen (i.e. 3% of mass addition), and fully oxidizing to obtain an iron chloride solution product.
Example 5
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 20% of content and 10% of acidity), stirring at 1000rpm, setting the temperature of a reaction kettle at 200 ℃, setting the working pressure at 1.0kPa, pumping 0.9g of oxygen (namely 3% of mass addition), and fully oxidizing to obtain an iron chloride solution product.
Example 6
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 30% of content and 15% of acidity), stirring is started, the rotating speed is 1000rpm, the temperature of the reaction kettle is set to be 180 ℃, the working pressure is 2.0kPa, 1.5g of oxygen is pumped (namely, the mass addition amount is 5%), and the ferric chloride solution product is obtained after full oxidation.
Example 7
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 5% of content and 5% of acidity), stirring at 1000rpm, setting the temperature of the reaction kettle at 180 ℃, setting the working pressure at 2.0kPa, pumping 0.6g of oxygen (namely, 2% of mass addition), and fully oxidizing to obtain an iron chloride solution product.
Comparative example 1
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 15% of content and 7% of acidity), stirring is started, the rotating speed is 1000rpm, the temperature of the reaction kettle is set to be 100 ℃, the working pressure is 5.0kPa, 0.6g of oxygen is pumped (namely, the mass addition amount is 2%), and the ferric chloride solution product is obtained after full oxidation.
Comparative example 2
A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method comprises the following steps:
into a 50mL autoclave was charged 30g (Fe 2 O 3 15% of content and 7% of acidity), stirring is started, the rotating speed is 1000rpm, the temperature of the reaction kettle is set to be 250 ℃, the working pressure is 0.5kPa, 0.6g of oxygen is pumped (namely, the mass addition amount is 2%), and the ferric chloride solution product is obtained after full oxidation.
Result detection
Determination of Fe in ferric chloride solutions obtained in the above examples and comparative examples by Potassium dichromate titration 3+ Content and Fe 2+ The content is as follows; the HCl content in the ferric chloride solutions obtained in the above examples and comparative examples was measured by an acid-base neutralization titration method.
Fe in the iron-containing waste hydrochloric acid is obtained through calculation 2+ The specific calculation formula is as follows:
conversion α= (1-m) 2 *W 2 (Fe 2+ )/m 1 *W 1 (Fe 2+ ))*100；
Wherein m is 1 And m 2 The total mass of the iron-containing waste hydrochloric acid before and after the reaction is respectively W 1 And W is 2 Fe before and after the reaction respectively 2+ Is added to the total mass content of (3).
The results are shown in Table 1.
TABLE 1 content of ferric chloride solution product ingredients and ferrous ion conversion
Fe 3+ Content/% HCl content/% Fe 2+ Conversion/%
Example 1 14.62 0.09 100
Example 2 9.06 0.26 99.64
Example 3 10.81 0.22 99.85
Example 4 12.94 0.20 99
Example 5 14.65 0.32 95.2
Example 6 19.36 0.34 96.8
Example 7 4.72 2.54 100
Comparative example 1 3.67 1.60 66.78
Comparative example 2 4.32 2.10 53.43
As can be seen from Table 1, the method for treating waste hydrochloric acid containing iron by catalytic oxidation according to the invention is specific to Fe 2+ High oxidation efficiency of Fe 2+ Not less than 95%; as can be seen from examples 1 to 7, the iron content, acidity, temperature, pressure of oxidation reaction and addition amount of oxygen in the iron-containing waste hydrochloric acid all affect Fe 2+ Is a conversion rate of (2); the reaction temperature in comparative example 1 was too low and the reaction pressure was too high, and it was not satisfied that Fe in the iron-containing spent hydrochloric acid 2+ The reaction heat conditions required for oxidation result in Fe 2+ The oxidation efficiency is low, and the conversion rate is low; the temperature of the oxidation reaction in comparative example 2 was too high, while the reaction pressure was too low, and Fe in the final iron-containing spent hydrochloric acid 2+ The conversion was also reduced, only 53.43%.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (10)

1. A method for treating waste hydrochloric acid containing iron by catalytic oxidation-free method is characterized by comprising the following steps:
introducing oxygen into waste hydrochloric acid containing iron to perform oxidation reaction to obtain ferric chloride solution; the reaction temperature is 150-200 ℃, and the reaction pressure is 1-3 kPa; no catalyst or oxidation auxiliary agent is added in the reaction process.
2. The method according to claim 1, wherein the iron content of the iron-containing waste hydrochloric acid is Fe 2 O 3 The content is 10-20%.
3. The method according to claim 2, wherein the iron content of the iron-containing waste hydrochloric acid is Fe 2 O 3 13 to 17 percent.
4. The method of claim 1, wherein the iron-containing spent hydrochloric acid has an acidity of 5 to 10%.
5. The method of claim 4, wherein the acidity of the iron-containing spent hydrochloric acid is from 6.5 to 8.5%.
6. The method of claim 1, wherein the oxygen is added in an amount of 1 to 3% of the mass of the iron-containing waste hydrochloric acid.
7. The method of claim 1, wherein the reaction temperature is 165 to 185 ℃.
8. The method of claim 1, wherein the reaction pressure is 1.5 to 2.5kPa.
9. The method of claim 1, wherein the oxidation reaction is performed with agitation.
10. The method of claim 1, wherein the ferric chloride solution after the oxidation reaction is used to preheat the iron-containing waste hydrochloric acid feed.
CN202211697523.7A 2022-12-28 2022-12-28 Method for treating iron-containing waste hydrochloric acid without catalytic oxidation Pending CN116216904A (en)

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CN202211697523.7A CN116216904A (en) 2022-12-28 2022-12-28 Method for treating iron-containing waste hydrochloric acid without catalytic oxidation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211697523.7A CN116216904A (en) 2022-12-28 2022-12-28 Method for treating iron-containing waste hydrochloric acid without catalytic oxidation

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