TWM558797U - Solidifying and manufacturing system of ferric tri-chloride hexahydrate - Google Patents

Abstract

A solidification manufacturing system for ferric chloride hexahydrate, comprising a waste iron acid containing hydrochloric acid, iron, or a ferrous chloride production device for reacting a raw material such as iron, hydrochloric acid or water to obtain a ferrous chloride solution, and supplying chlorine The ferrous oxide and the oxidant react to obtain an oxidizing device for the ferric chloride liquid, a vacuum device, and a low-temperature drying device. The vacuum vacuum device is configured to operate in a vacuum environment with a working temperature range of 30 ° C to 100 ° C for heating the ferric chloride liquid in the closed vessel to obtain distilled waste water and concentrated ferric chloride liquid. The low temperature drying device comprises a freezing compartment and a drying unit for removing moisture in the freezing compartment, the freezing compartment being configured to operate in a low temperature drying environment with an operating temperature range of -20 ° C to +20 ° C for the aforementioned concentration The subsequent ferric chloride liquid exotherms in the freezer compartment and crystallizes during the exothermic process to obtain a solid of ferric chloride hexahydrate having a purity of 60% to 99%.

Description

Curing manufacturing system for hexahydrate ferric chloride

The present invention relates to a ferric chloride hexahydrate, in particular to a solidification manufacturing system of ferric chloride hexahydrate.

Ferric chloride hexahydrate (FeCl ₃ .6H ₂ O) has a strong substitution effect on various metal materials. Therefore, it is widely used in circuit etching of electronic products, etching of metal parts, or as water. Treatment agent, chlorination agent in metallurgical industry, oxidant and mordant in dye industry, etc.

The preparation method of the conventional hexahydrate ferric chloride disclosed in the Chinese Patent No. CN104003451, the Chinese Patent No. CN106745321, and the Chinese Patent No. CN102701290, mainly the ferric chloride After the solution FeCl _{3 was} concentrated by evaporation, it was cooled and collected as solid FeCl ₃ •6H ₂ O. The difference between the aforementioned patents is:

The CN104003451 patent uses anhydrous ferric chloride FeCl ₃ (solid granules) as a raw material, and extracts a concentrated solution of FeCl ₃ using an organic solvent, and then collects solid FeCl ₃ •6H ₂ O by a centrifuge. Since the raw material itself is already a finished product and includes an organic solvent, not only is the cost high, but long-term inhalation may adversely affect the operator's human body.

In the patent CN106745321, a solid solution of ferrous chloride FeCl _{2 is} added to prepare a FeCl ₂ solution, and the FeCl ₂ solution is oxidized to a FeCl ₃ solution by using sodium nitrite as an oxidizing agent, and concentrated by evaporation and charged into a solid seed crystal FeCl _{3 for} cooling. Crystallization, a suspension is obtained, and the suspension is solid-liquid separated to obtain a solid finished FeCl ₃ •6H ₂ O _(s) . Since it is required to input solid crystal seeds and utilize nitrogen-containing oxidant as a raw material, it is not only costly, but also generates nitrogen-containing waste, which will have an impact on the environment.

In the patent CN102701290, the FeCl ₂ solution is prepared by adding waste acid liquid and iron, and then the FeCl ₂ solution is oxidized into FeCl ₃ solution by using chlorine gas as an oxidizing agent, and the temperature is maintained not higher than 80 ° C, and then stirred and cooled to 20 ° C to 45 ° C. Then, the solid crystal seed FeCl _{3 is} put into a supersaturated solution of FeCl ₃ , and then left to stand in an incubator at 0 ° C ~ 15 ° C for 5-8 hours to obtain a solid finished FeCl ₃ • 6H ₂ O _(s) . Since the seed crystals are also required to be input, and the temperature control thereof is complicated, the process is complicated.

Therefore, the object of the present invention is to provide a curing manufacturing system for ferric chloride hexahydrate which can meet the environmental protection requirements and can simplify the process and improve the product quality.

Therefore, the solidification manufacturing system of the novel hexahydrate ferric chloride comprises a ferrous chloride manufacturing device, an oxidizing device, a vacuum vacuum device, and a low temperature drying device.

The ferrous chloride production apparatus includes a reaction vessel for supplying a waste acid solution containing hydrochloric acid, iron, or a raw material such as iron, hydrochloric acid or water, and reacting in the reaction vessel to obtain a ferrous chloride solution.

The oxidizing device comprises an oxidation vessel for reacting the ferrous chloride liquid and the oxidizing agent in the oxidation vessel to obtain a ferric chloride liquid having a weight percentage of iron ions of m.

The vacuum vacuum device comprises a closed container configured to operate in a vacuum environment with a working temperature of 30 ° C to 100 ° C for heating the ferric chloride liquid in the closed container to obtain distilled waste water, and A ferric chloride solution having a concentration of n by weight of iron ions after concentration, wherein n>m.

The low temperature drying device comprises a freezing compartment and a drying unit for removing moisture in the freezing compartment, the freezing compartment being configured to operate in a low temperature drying environment with an operating temperature range of -20 ° C to +20 ° C for the aforementioned concentration The subsequent ferric chloride liquid exotherms in the freezer compartment and crystallizes during the exothermic process to obtain a solid of ferric chloride hexahydrate having a purity of 60% to 99%.

The effect of the novel is that the novel type does not contain a sulfate or an organic solvent, and can form an environmentally-friendly regenerated product using a waste acid solution, and the obtained concentration of ferric chloride is stable, and the process can meet environmental protection requirements and can simplify the process. And improve product quality.

Referring to Fig. 1, an embodiment of a solidification manufacturing system for a novel ferric chloride hexahydrate includes a ferrous chloride manufacturing apparatus 1, an oxidation unit 2, a vacuum chamber 3, and a low temperature drying unit 4.

The ferrous chloride producing apparatus 1 includes a reaction vessel 11, a hydrochloric acid vessel 12 connected to the reaction vessel 11, and an air neutralization unit 13 connected to the reaction vessel 11 and the hydrochloric acid vessel 12. The reaction vessel 11 contains a waste acid liquid containing hydrochloric acid, an iron ore material, or a natural iron material (such as iron powder, iron ore), hydrochloric acid, water, and the like. The hydrochloric acid container 12 is used to supply hydrochloric acid required for the reaction process. The air neutralization unit 13 is for introducing outside air, and mixing the air with the gas discharged from the reaction vessel 11 and the hydrochloric acid vessel 12 to achieve a neutralization effect.

The oxidizing device 2 includes an oxidation vessel 21 that communicates with the reaction vessel 11, a recovery unit 22 that communicates with the oxidation vessel 21, and an air neutralization unit 23 that communicates with the oxidation vessel 21 and the recovery unit 22. The oxidation vessel 21 is for accommodating the reactants and oxidant of the reaction vessel 11, and converting the ferrous chloride solution into a ferric chloride solution. The recovery unit 22 is used to store the ferrous chloride solution and recover excess chlorine. The air neutralization unit is configured to introduce outside air, and mix the air with the gas discharged from the oxidation container 21 and the recovery unit 22 to achieve a neutralization effect.

The vacuum chamber 3 includes a sealed container 31 connected to the oxidation vessel 21, a condenser 32 connected to the sealed vessel 31, a vacuum tank 33 communicating with the condenser 32, and a condenser 32 connected thereto. A water pump 34 of the sealed container 31. The hermetic container 31 is configured to operate in a vacuum atmosphere with an operating temperature range of 30 ° C to 100 ° C and to accommodate the reactants of the oxidation vessel 21 . The condenser 32 is for condensing moisture generated when the reactants are heated in the sealed vessel 31, so that the water vapor forms distillation waste water. This vacuum tank 33 is used to collect the aforementioned distillation wastewater. The water pump 34 generates a flow of water flushed from the top to the bottom, and further suctions the gas in the condenser 32 and the sealed container 31, so that the sealed container 31 is constructed in a vacuum environment.

The low temperature drying device 4 includes a freezing compartment 41, a heat exchange unit 42, and a drying unit 43. The inside of the freezer compartment 41 is adapted to be provided with a number of dies 5 which contain the aforementioned reactants. The heat exchange unit 42 is used to cool the freezer compartment 41. The drying unit 43 has a number of fans 431 mounted in the freezer compartment 41 for removing moisture in the freezer compartment 41. Thereby, the freezer compartment 41 is constructed to have a low temperature drying environment with an operating temperature range of -20 ° C to + 20 ° C.

Referring to FIG. 1 and FIG. 2, a manufacturing process of the present invention will be described below in conjunction with the embodiment:

[Chlorine chloride process 6]

The novel ferrous chloride liquid process 6 has two embodiments.

In the first embodiment, a spent acid solution containing hydrochloric acid, iron ore, and iron are added to the reaction vessel 11, and after aeration heating, heavy metal precipitation, and filtration, an industrial grade ferrous chloride solution is obtained.

Second Embodiment: A natural iron material (e.g., iron powder, iron ore), hydrochloric acid, and water are added to the reaction vessel 11 to obtain a ferrous chloride solution in accordance with the specifications of the tap water. In this embodiment, the iron material is bounded by 85% to 98% of the iron material, the hydrogen chloride is 32% by weight of hydrochloric acid, and water is used as the raw material.

In the process, both the above embodiments can control the ratio of iron, hydrogen chloride and water through the ferrous chloride manufacturing device 1, and the pH is between 0 and 5, and the process temperature is between 30 ° C and 90 ° C. °C, and the process time between 8 and 36 hours of process conditions, the ferrous chloride (Fe ²⁺ ) weight percentage concentration of 30% ~ 36% of ferrous chloride solution.

Chemical reaction formula: Fe+2HClàFeCl ₂ +H ₂

It is worth noting that in the ferrous chloride liquid process 6, in addition to the ferrous chloride solution, nitrogen oxides such as hydrochloric acid gas and hydrogen gas are generated, and no excess waste water is generated. The nitrogen oxides such as hydrochloric acid gas and hydrogen gas are further neutralized with the air in the air neutralization unit 13 to comply with environmental regulations and directly discharged to the outside world.

[Oxidation Process 7]

Introducing the ferrous chloride solution into the oxidation vessel 21, adding an oxidizing agent, and passing through the oxidizing device 2, obtaining a weight percentage of iron ions (Fe ³⁺ ) in a process condition of a redox time of 4 to 10 hours. A ferric chloride solution of concentration m. In this embodiment, m = 30% to 48%.

The gasification agent may be classified into two types of embodiments, such as liquid chloride, sodium chlorate or potassium hydroxide, in combination with an industrial grade ferrous chloride solution or a ferrous chloride solution conforming to the tap water specification.

The first embodiment: adding sodium chlorate (NaClO ₃ ) or potassium hydroxide (KOH) to the industrial grade ferrous chloride solution to obtain a weight concentration of iron ions (Fe ³⁺ ) of m bound to 30 %~48% ferric chloride solution.

Chemical reaction formula 1: 7FeCl ₂ +NaClO ₃ +6HClà7FeCl ₃ +3H ₂ O+Na ⁺

Chemical reaction formula 2: 2FeCl ₂ +2HCl+6KOHà2Fe(OH) ₃ ^­ +6KCl+H ₂

In the second embodiment, liquid chlorine is added to the ferrous chloride solution conforming to the specification of the tap water to obtain a ferric chloride solution having a concentration of iron ions (Fe ³⁺ ) of 30 to 48% by weight.

Chemical reaction formula: 2FeCl ₂ +Cl ₂ à2FeCl ₃

In the above two embodiments, the obtained ferric chloride liquid component can be controlled by the oxidation device 2, wherein the redox value (ORP) is between 600 and 1200, and the ion free rate (acid) is between 0.1% and 3 %, insoluble matter (s/s) content of 0.02% by weight.

It is worth noting that in the oxidation process 7, in addition to the ferric chloride liquid, nitrogen oxides such as hydrochloric acid gas and hydrogen gas, excess chlorine gas, and oxidizing gas are generated, and no excess waste water is generated. The excess chlorine gas and oxidizing gas are recovered by the recovery unit 22. The nitrogen oxides such as hydrochloric acid gas and hydrogen gas, and residual chlorine gas and oxidizing gas are further neutralized with the air in the air neutralization unit 23, and then can be directly discharged to the outside world in compliance with environmental regulations.

[Vacuum vacuum concentration process 8]

Introducing the ferrous chloride liquid into the sealed container 31, and in the vacuum atmosphere, the operating temperature is between 30 ° C and 100 ° C, and the concentration time is between 4 and 8 hours. Next, the water in the ferric chloride liquid is evaporated into moisture, and the water vapor is condensed through the condensation pipe 32 to form distilled waste water having a pH value of 1 to 3, and is concentrated in the vacuum drum 33. The ferric chloride liquid is concentrated by evaporation of water to obtain a ferric chloride solution having a weight concentration of iron ions (Fe ³⁺ ) of n, and the liquid color thereof is reddish brown and n>m. In the present embodiment, n is 48% to 63%, and if the production of the ferric chloride liquid after concentration is 11KL, the distillation waste water produced is 1 to 4 KL.

In the present embodiment, the negative pressure vacuum environment utilizes a water pump 34 that communicates with the sealed container 31, the condensation tube 32, and the vacuum tub 33 to generate a flow of water that is flushed from the top to the bottom, and the condensation tube 32, the The gas in the hermetic container 31 generates a suction effect, so that the hermetic container 31 is constructed in a vacuum environment. Thereby, the boiling point of the ferric chloride liquid under the negative pressure state is lowered, and evaporation can be performed under the conditions of an operating temperature of 30 ° C to 100 ° C.

It is worth noting that in the vacuum negative pressure concentration process 8, no excess waste is generated except for the concentrated ferric chloride liquid and the distilled waste water. After the above-mentioned distillation wastewater is neutralized by the acid and alkali of the raw water (that is, the natural water body), it can comply with environmental regulations and directly discharge the outside.

In addition, the ferrous chloride solution may be subjected to the vacuum negative pressure concentration process 8 before performing the oxidation process 7, to obtain a ferrous chloride (Fe ³⁺ ) weight percentage concentration of 48% to 63% of chlorination. The ferrous liquid, and then the obtained ferrous chloride liquid is further subjected to the foregoing oxidation process 7 and the vacuum negative pressure concentration process 8, whereby the iron ion (Fe ³⁺ ) weight percentage concentration of the ferric chloride solution is increased. And, in combination, the iron ion (Fe ³⁺ ) weight percentage of the concentrated ferric chloride solution is increased.

[Freeze-drying curing process 9]

The concentrated ferric chloride liquid is allowed to stand in the molds 5 in the freezer compartment 41, and the ferric chloride liquid is crystallized during the standing of the freezer compartment 41.

Since the ferric chloride liquid exotherms during the crystal growth process, in the present embodiment, the inside of the freezer compartment 41 is cooled to -20 ° C to +20 ° C by the heat exchange unit 42 , and the drying unit is used. These fans 431 of 43 exclude moisture in the freezer compartment 41. Thereby, the freezer compartment 41 is constructed to have a low temperature drying environment with an operating temperature range of -20 ° C to + 20 ° C.

Thereby, under the low temperature action and the drying effect of the low temperature drying environment, the water vapor generated by the iron chloride liquid in the heat release process can be condensed, and after the condensed water gas is discharged to the outside, the drying effect is improved. The ferric chloride solution is maintained at an operating temperature of -20 ° C to +20 ° C for continuous crystal growth, and the curing time of the ferric chloride is controlled by the low temperature drying device 4, and the concentrated ferric chloride solution is frozen and dried. After 6~8 hours, after standing for 4~16 hours, it can be stripped to obtain a solid of ferric chloride hexahydrate (FeCl ₃ .6H ₂ O) with a purity of 60%~99%.

It is worth noting that the above-mentioned weight percentage of ferric chloride depends on the concentration of iron ion (Fe ³⁺ ) in the ferric chloride solution in [Oxidation Process 7], and the chlorination in [Vacuum Negative Pressure Concentration Process 8]. The iron ion (Fe ³⁺ ) weight percent concentration of the molten iron.

And the foregoing hexagonal water ferric chloride solid can be matched with the design of the mold 5, and presents a golden yellow block or a yellow-red block with a complete appearance and no sharp angle, and the composition of the redox value (ORP) is between 800 and 1000. The ion free rate (acid) is between 0.1% and 3%, the insoluble matter (s/s) is 0.02% by weight, and the chlorine concentration is between 41% and 36%.

Referring to FIG. 1 and FIG. 3, another curing manufacturing process of the present invention will be described below in conjunction with this embodiment:

Referring to FIG. 1 and FIG. 3, it is substantially the same as the foregoing manufacturing process, and also includes [ferrous chloride liquid process 6], [oxidation process 7], [vacuum negative pressure concentration process 8], and [freeze drying curing process 9 ], the difference lies in:

After [vacuum vacuum concentration process 8] and [freeze-drying process 9], [granulation process 10] is also included.

Mainly, the concentrated ferric chloride liquid is placed in a granulator (not shown), and the suspended crystals of the ferric chloride and the liquid residual material are obtained. Then, the crude suspended iron chloride crystal is formed by an extrusion granulator (not shown) or an air granulator (not shown), and then the freeze-drying curing process 9 can be carried out, and the above-mentioned low-temperature drying is performed. In the environment, the mixture is freeze-dried for 2 to 4 hours to obtain a granular solid of ferric chloride hexahydrate having a purity of 60% to 99%. After the liquid residue can be recovered, the concentrated ferric chloride solution can be added, and the freeze-drying curing process 9 can be repeated to obtain a solid of ferric chloride having a purity of 60% to 99%.

Since the general knowledge in the art can infer the details of the expansion based on the above description, it will not be explained.

Through the above description, the advantages of the foregoing embodiments can be summarized as follows:

1. The new type does not contain sulfate or organic solvent, and the by-products such as hydrochloric acid gas, hydrogen and other nitrogen oxides, and the distillation wastewater are further treated with air, or neutralized by the raw water acid and alkali, and then can be environmentally friendly. The regulations are directly discharged from the outside world, which not only has no pollution to the environment, but also meets environmental protection needs.

2. The novel can form an environmentally-friendly regenerated product by using the waste acid solution, and the freeze-drying curing process 9 does not require seeding, and the cost is low.

3. The present invention concentrates ferric chloride liquid in a vacuum atmosphere, which not only reduces the boiling point of the ferric chloride liquid, but also lowers the operating temperature, simplifies the process, and the process time, and the obtained weight of ferric chloride is 100. The concentration is stable.

4. Furthermore, the novel is a freeze-drying curing process in a low-temperature drying environment, which can improve the drying effect and improve the product quality through the low-temperature drying and drying effects of the aforementioned low-temperature drying environment, so that the finished product is not easily deliquescent and easy to store. It is convenient for transportation and has a long shelf life.

5. Using the aforementioned low-temperature drying environment to control the curing time of the concentrated ferrous chloride solution to achieve the mass production benefit.

However, the above is only the embodiment of the present invention, and when it is not possible to limit the scope of the present invention, all the simple equivalent changes and modifications according to the scope of the patent application and the contents of the patent specification are still This new patent covers the scope.

1‧‧‧ Ferrous chloride manufacturing equipment
11‧‧‧Reaction container
12‧‧‧ hydrochloric acid container
13‧‧‧Air neutral unit
2‧‧‧Oxidizer
21‧‧‧Oxidized container
22‧‧‧Recycling unit
23‧‧‧Air Neutral Unit
3‧‧‧Negative vacuum device
31‧‧‧Contained container
32‧‧‧Condensation tube
33‧‧‧vacuum barrel
34‧‧‧Water pump
4‧‧‧Low temperature drying device
41‧‧‧Freezer compartment
42‧‧‧Heat exchange unit
43‧‧‧Drying unit
431‧‧‧Fan
5‧‧‧Mold
6‧‧‧Nitrile chloride process
7‧‧‧Oxidation process
8‧‧‧ Vacuum negative pressure concentration process
9‧‧‧Freeze-drying curing process
10‧‧‧granulation process

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a schematic diagram illustrating an embodiment of the novel solidification manufacturing system of ferric chloride hexahydrate; 2 is a flow chart illustrating a manufacturing flow of the embodiment; and FIG. 3 is a flow chart illustrating another manufacturing flow of the embodiment.

Claims (9)

A solidification manufacturing system for ferric chloride hexahydrate comprises: a ferrous chloride manufacturing device comprising a reaction vessel for waste acid liquid containing hydrochloric acid, iron, or iron, hydrochloric acid, water and the like, in the reaction vessel Internal reaction to obtain a ferrous chloride solution; an oxidation device comprising an oxidation vessel for reacting the ferrous chloride solution and the oxidant in the oxidation vessel to obtain a ferric chloride solution having a weight percentage of iron ions of m; a vacuum chamber comprising a sealed container configured to operate in a vacuum environment with a working temperature of 30 ° C to 100 ° C for heating the ferric chloride liquid in the closed vessel to obtain distillation wastewater. And a concentrated ferric chloride solution having a weight percentage of iron ions of n, wherein n>m; and a cryogenic drying apparatus comprising a freezing compartment and a drying unit for removing moisture in the freezing compartment, The freezer compartment is configured to operate in a low temperature drying environment with an operating temperature range of -20 ° C to + 20 ° C, and the concentrated ferric chloride liquid is exothermic in the freezing compartment, and crystallized during the exothermic process to obtain a purity boundary. 60%~99% of Liushuisan Ferric chloride solid. The solidification manufacturing system of ferric chloride hexahydrate according to claim 1, wherein the ferrous chloride producing apparatus further comprises a hydrochloric acid container connected to the reaction vessel, wherein the hydrochloric acid container is used for supplying a reaction process. hydrochloric acid. The solidification manufacturing system of ferric chloride hexahydrate according to claim 2, wherein the ferrous chloride manufacturing apparatus further comprises an air neutralization unit connected to the reaction vessel and the hydrochloric acid container, the air neutralization unit It is used for introducing the outside air, so that the hydrochloric acid gas and hydrogen gas generated in the reaction vessel and the hydrochloric acid container during the reaction are directly discharged to the outside after being neutralized with air. The solidification manufacturing system of ferric chloride hexahydrate according to claim 1, wherein the oxidizing device further comprises a recovery unit connected to the oxidation vessel, the recovery unit is configured to store the ferrous chloride solution, and recover the Excess chlorine and oxidizing gas generated in the oxidation vessel during the reaction. The solidification manufacturing system of ferric chloride hexahydrate according to claim 4, wherein the oxidizing device further comprises an air neutralization unit connected to the oxidation vessel and the recovery unit, the air neutralization unit being used for introducing the outside The air, the hydrochloric acid gas, hydrogen gas, excess chlorine gas and oxidizing gas generated in the oxidation process during the reaction process are directly discharged to the outside after being neutralized with air. The solidification manufacturing system of ferric chloride hexahydrate according to claim 1, wherein the vacuum vacuum device further comprises a condensation tube connected to the sealed container, and a vacuum barrel connected to the condensation tube, the condensation The tube is used for condensing water and gas generated when the ferric chloride liquid is heated in the closed container, so that the water gas forms distillation waste water, and the vacuum tank is used for collecting the foregoing distillation waste water. The solidification manufacturing system of ferric chloride hexahydrate according to claim 6, wherein the vacuum vacuum device further comprises a water pump connected to the condensation tube and the sealed container, the water pump generating a water flow flushed from the top to the bottom Further, a suction effect is generated on the gas in the condenser tube and the sealed container, and a vacuum atmosphere is formed in the sealed container. A solidification manufacturing system for ferric chloride hexahydrate according to claim 1, wherein the low temperature drying device further comprises a heat exchange unit for cooling the freezer compartment. A solidification manufacturing system of ferric chloride hexahydrate according to claim 8, wherein the drying unit has a number of fans installed in the freezer compartment.