TWI257919B - Method for producing sulfuric acid compound from solution containing chloride and production method thereof - Google Patents

Abstract

The present invention provides a method for producing sulfuric acid compounds from a waste acid solution, particularly a method for producing iron (II) sulfate, iron sulfide, zinc sulfate from an acid-washing solution. The method mainly comprises: adding a suitable amount of sulfuric acid into a reactor contained a solution of ferrous chloride and zinc chloride; using substitution reactions to produce iron sulfide and zinc sulfate; transporting the produced iron sulfide and zinc sulfate to a separator; adding an organic solvent into the separator and precipitating out the zinc ions; transporting the zinc-containing organic compounds to a zinc sulfate reducing device; using an acid precipitation method to produce zinc sulfate with commercial values; transporting the iron sulfide remained in the separator to an iron (II) sulfate reactor to be converted into iron (II) sulfate with commercial values by an oxidation process. Thus, the economic value of waste solution can be effectively increased, and the environmental quality requirements can be ensured.

Description

Emperor 9111 times 1257919 Amendment 曰5, invention description (1) The present invention relates to a method for treating and recovering sulphation from a spent acid solution 4, especially a waste which can contain vapors from within The acid solution produces a method of producing a sulfuric acid compound such as iron sulfate, ferrous sulfate or zinc sulfate. " Press, metal substances (such as iron) s in the air will inevitably occur gasification reaction, that is, the metal is commonly referred to, and the industry generally f acid to clean the surface of the oxidized metal, but After cleaning, it will be accompanied by the formation of a quality, which is a waste acid solution containing chloride inside. These waste acid solutions are not only time-consuming and labor-intensive in processing, but also form a large burden on environmental protection:: Electroplating tank discharge The waste acid solution contains not only chlorine, but also toxic substances such as zinc chloride, which are more difficult and troublesome to handle than the internal acid solution of the internal ΐ ΐ , , , , , , The cost of the required cost is higher; also||In the method of =; not only the production process is cumbersome, but also the main product is difficult to recycle the product to reduce the processing cost, and the output is recovered. Obtaining a higher quality condition and controlling the consistency of the operation size during the production process : ': Degree tk is used to effectively reduce the defect of low recovery of crystal grains, product acidity is too high, or hydrochloric acid production More Lord invention! Ming focus. Therefore, in the solution, the zinc chloride and the ferrous chloride crystal are produced under the conditions of the production of the chloride from the production; the fifth page 1257919

V. Description of the invention (2) Emperor 9in··

An appropriate organic solvent separates zinc hydride and gasified ferrous iron, and the recovered product is not only highly purified, but also has a commercial value standard on the market. The secondary object of the present invention is to provide a method for producing a sulfuric acid compound from a solution containing vapors therein, which can be controlled by a strict control under a lower cost salt production condition. The process can be set in a stable state to ensure the sulfur-sulfurization rate. Another object of the present invention is to provide a method for producing a sulfuric acid compound from a solution containing chloride, which can contain chlorine from the inside. The high-yield hydrochloric acid is produced in the waste acid solution of the chemical and ferrous chloride. Another object of the present invention is to provide a method for producing a sulphate compound from a solution containing chloride in a solution, which can separate ferrous chloride and zinc hydride from a spent acid solution and borrow This produces a more commercially valuable filter cake, which in turn reduces the cost of production.发明 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 【 A method for producing ferrous iron, iron sulfate or zinc tetraphosphate and a production device thereof. 1 The present invention uses a precise and unique automatic control method to produce a high quality metal salt product under high yield conditions of hydrochloric acid. The basic method 2 uses an air blowing device to dissolve the hydrochloric acid mixed in the sulfuric acid solution. = and excess water is blown out. However, if you want to create a price that can be connected to the market =

1257919

Case 1 5, invention description (3) value recovery product 'need to design a set of 裎 及 and P 捋 妆 π 丄 丄 丄 丄 丄 丄 丄 丄 丄 丄 丄 丄 夜 夜 夜 夜 夜 夜 夜 夜 夜 夜 亚 亚 亚 亚Control sulfuric acid, air, waste acid solution 'energy:=' : ί can also maintain a constant equilibrium under the relative relationship of various variables; = the law 'can achieve the maximum yield and height of the final product; in order to determine the production process It is necessary to control the daily flow of the production process in a state of release, so that the liquid level, the sulfuric acid concentration, and the air flow rate of the blowing must be constant, so as to ensure the uniform growth of the crystal grains. In order to obtain a filter cake of commercial value. It is hoped that the change of acidity in the reactor will lead to different changes, and the precipitation rate will also be affected by the anti-column cry, w Λ w 符 生 生 生 生 生 t t t , , , , , , , , , , , , And the blown air flow rate of the shirt is n if the number - straight in the normal state of the variable state line 'and the relative output quality is poor. Therefore, the invention mainly provides uniform production of uniform crystal grains in the production process, and allows subsequent filtration and fluidity to increase ~ 'relatively precipitates higher quality and commercial value of recovered product 'I' at a constant temperature And the air flow shape is 'to maintain the appropriate acidity in the reactor, thereby producing a volume of gray, easy to filter and quickly settled crystal grains. On the contrary, if the acidity in the reactor is maintained too high, the crystal grains produced in the process will be fine, white, not easy to settle, not easy to flow and difficult to filter. If temperature and air flow are changed, then Make the situation more sub-chemical. On the other hand, 'If the acidity in the reactor is kept too low', then the grain size of the output will be suddenly large and small, and the yellow color will appear. ^生^_1 1257919 V. Invention Description No. 91113316 (4)

It is difficult to precipitate and contains excess hydrochloric acid. If the temperature and air flow change again, the situation will be worsened. The acidity in the solution reactor changes more frequently (temperature and air flow are also), and the larger the volume of the crystal grain is, the more uneven the result is. Will lead to a series of operational problems. ^ The control system of the manufacturing process must be able to control the liquid level, temperature, sulfuric acid concentration and air flow in the solution. These must be maintained in a good agitation situation. There must be a constant relationship with each other. Any change in the parameters will change the rate and size of the formation of crystal grains, thus affecting the uniformity of the solid particles and the filtration results of the produced products. ~θ μ, input air flow rate is about 600CFM, temperature is below Fahrenheit (English), so that it can produce other parameters with high quality and can control these variable parameters. The computerized control of the sensory system is achieved by manual means to control the filtration produced by the acid solution. A method that can be separated from the ferrous sulfate / to the separation is to maintain the 55% weight in the mixture. Between 60% by weight, 1,20 0 CFM (cubic inches per minute) to 1 180 degrees, and the liquid level in the reactor is 3 〇 „ can be used to ensure the recovery of commercial value in the case of high output of hydrochloric acid However, as long as the relationship between them is kept constant, and the effective conditions of the same method, these parameters should be controlled by the instrument to input the signal into the computer, but if there is enough manpower, it can also be used. Increase the zinc from the zinc plating, with the commercial economic price A, this y: acid = compound separated from the zinc silicate with an organic" zinc ions from the sulfuric acid ^

[Details] Poor HU13316 V. Inventive Note (5) Come out to become an organic compound, and divide it into more than eight, and use the stone to co-organize _ out of the g-zinc organic compound and reuse slave I or hydrochloric acid to make the organic compound The separation of zinc sulfate is achieved. (4) Separating the western zinc ions, thereby

1257919 In order to give your review board a more advanced understanding of the efficacy and a detailed graphical explanation, this booklet describes a method for producing a product in a waste acid solution of a hydrazine compound. A substance such as waste acid dissolved and vaporized ferrous iron produced after the ferrous chloride metal object, such as a gasified ferrous iron and 3% by weight of hydrochloric acid. Zinc plating tank (or aluminum electroplating plant), then ferrous chloride, hydrochloric acid and water, zinc. Please refer to Figure 1 for a schematic diagram; as shown in the figure, the production process of this step is based on pickling. In the first step, the gold gas ions are introduced from a metal chloride molecular acid > trough liquid into the solution reactor 1 through a rate. ^Structural characteristics of the invention and the desired effect < 哉 谨 谨 谨 谨 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 最佳 = = = = = = = = = = = = = The iron may contain water, hydrochloric acid-like waste acid solution containing about 38% by weight of another 'if the pickling solution is from the pickling solution, in addition to containing the above, may also include about 10% by weight. Chlorine The construction of a preferred embodiment of the invention can basically comprise whether two or three solutions have a zinc-containing material and the chloride is first mixed with hot sulfuric acid to release it. Waste metal line containing metal gasification 1 2 (first line) continuous or sequential waste acid solution before starting to feed, the solution case number 91113316

1257919 In reactor 10, sulfuric acid has been injected through a line 丨4 (eleventh line). The concentration of sulfuric acid is preferably maintained at about 93% by weight (93% w·t·%) before mixing with the metal hydride. It is best to heat to between 6 and 3 degrees Fahrenheit. Within the anti-corruption cry 10, the concentration of sulfuric acid will be strictly monitored and controlled, and can be maintained between -% and 98% by weight, as in the present embodiment, controlled at 59 w·t·%, and the reaction in the reactor 10 The temperature is between 60 and 300 degrees Fahrenheit, for example in the present embodiment controlled at 180 degrees Fahrenheit. Of course, the spent acid solution must be filtered prior to the feed and remove any unwanted materials such as contaminants and carbon.

In order to maintain the concentration of sulfuric acid in the reactor constant at 59 w·t·%, the concentration of sulfuric acid needs to be constantly monitored and controlled by the instrument when the sulfuric acid is introduced into the reactor 1 through the line 14. In order to ensure the consistency of the acid concentration in the solution reactor 1, the reactants must be heated to a temperature of 18 ° F and continuously reacted to the solution via a mixing nozzle or a stirring device 5 installed in the solution reactor 10 . The sulfuric acid and the waste acid solution in the crucible 1 are stirred to accelerate the mixing and reaction of the reaction materials. The gasified ferrous iron, zinc chloride and sulfuric acid are reacted according to the reaction formulas (1) and (2) to form hydrochloric acid, ferrous sulfate and zinc sulfate.

(1) FeC12+H2S04 = FeS04+2HCl (2) ZnC12+H2S04 = ZnS04+2HCl When the substance in the solution reacts, the air stream is sent to the reactor 1 via a line 13 (second line). The input air flow rate must be accurately controlled to a certain value according to objective conditions such as the size of the respondent 10, such as 1 20 0 CFM to 1 600 00 CFM in this embodiment. The blown air flow rate will pass through a line 丨8 (third line) at a certain rate after passing through the solution reactor 10.

1257919 J No. 91113316

V. INSTRUCTIONS (7) The port brings hydrochloric acid and excess water vapor into an absorption system. As shown in this example, ^ 616 is its main equipment, and the salt and the excess water are relocated in this system. And recycling. In the continuous operation mode, the concentration of hydrochloric acid carried by the air flow is about 25 wt.% to 29 wt.%. At this time, an appropriate amount of water can be added to the pipeline through a line 19 (the nineteenth line). Or directly into the absorption tower 16 , 'to control the concentration of hydrochloric acid near the azeotrope concentration, that is, about 2 1 w · t · % is the best, this concentration is the pickling solution of the steel metal pickling The general concentration. The water and hydrochloric acid in the recovery column 16 will be guided to reflux via a line 2 1 (fourth line) to a heat exchanger 2 that can use water, air or other thermal conductivity as a cold medium. The hydrochloric acid will be cooled to a suitable temperature at this time, for example, 11 degrees Fahrenheit in the present embodiment, and the hydrochloric acid having a concentration of 21·〇w·t. % is collected into a hydrochloric acid collection tank 2 via a line 22. 2 5 in. In addition, the water vapor and the uncollected hydrochloric acid, also having a concentration of about 21·〇·····, are recycled to the absorption tower 16 via a line 24 (the eighteenth line), and via a line 26 ( The fifth line) is refluxed to the solution reactor 10. An air blowing device 28 will be installed on the line 26, and in addition to increasing the power in the push line 26, the pressure in the solution reactor 1 can be increased to 3 〇π (inch) water column height. Therefore, in another embodiment of the present invention, the line 13 for conveying air flow may also be combined with the line 26 having the blowing device 28. The amount of hydrochloric acid carried by the blown gas stream in the reactor is determined by the temperature of the blown gas stream, although the use of a higher concentration of sulfuric acid allows the reactor to be operated.

Page 11 Case No. 91113316 1257919 Amendment 5, Invention Description (8) The temperature is lowered, but in this embodiment, it is recommended to use a higher air because the temperature of the air will trap a larger amount of hydrochloric acid, and the temperature will also decrease. The temperature at which the reactants are allowed to flow in the solution reactor enthalpy must be lower than the boiling point of hydrochloric acid of 23 ° F or the boiling point of the two phases of 227 · 4 degrees, and the circulating hydrochloric acid in the absorption tower 16 needs to be cooled to 60 ° F. Between 120 degrees, for example 110 degrees here, this is advantageous for the collection of hydrochloric acid. Controlling the concentration of hydrochloric acid in its azeotropic concentration will reduce the amount of hydrochloric acid in the reflux, thereby increasing the amount of hydrochloric acid recovered in the first cycle, so that most of the hydrochloric acid obtained by the learning reaction is recycled in the first step of the process, The unique place is that the air stream will take hydrochloric acid and water vapor from the solution reactor 1 and be taken up by the absorption system containing an absorption tower 16 to absorb and reduce most of the water and water, regardless of the waste. The acid solution is a waste acid solution containing ferrous ferrous oxide or only ferrous chloride. The air flow rate must be precisely controlled so that the hydrochloric acid collected by the air flow is brought back to the solution reactor 10 together. Since this air is maintained in a continuous cycle, any hydrochloric acid that has not been collected will be sent to the reactor 10 without any hydrochloric acid escaping into the atmosphere, so the process is very helpful for the absorption of hydrochloric acid, and for the air pollution Significant improvement. Moreover, since the air flow rate is precisely designed, the present invention only needs to use a minimum number of absorption towers 16 processes and purposes, thereby greatly reducing equipment and operation, adding sulfuric acid to the solution reactor 10 to replace the gas. The post-ion gas temperature is 5 and higher. The temperature in the water-hydrochloric acid is the first time in the process of the production process. The appropriate method is used, and then the hydrochloric acid-containing zinc acid waste acid solution can be used to return the unreceived flow rate back to the solution. Control and complete the cost. Sulfuric acid

Page 12 1257919 ^ ' · • _ Case No. 91113316_年月日日__ Amendment _ V. Description of invention (9) Iron (first sulfuric acid compound) will precipitate and produce, solution reactor 1 can be used by brother The production line 3 2 (sixth line) removes the ferrous sulfate product, sulfuric acid and water from the solution reactor 10 and directs it into a separator 34 which can be used to sulphuric acid from water and sulfuric acid. The iron is separated, and the treated water and sulfuric acid are refluxed to the solution reactor 1 via a line 3 6 (twelfth line), which is the second step of the invention. The aqueous solution of ferrous sulfate produced in the second step is guided into a ferric sulphate reaction 3 8 (second sulphuric acid compound reactor) via a line 4 第九 (ninth line), and a feed line 42 is utilized (tenth Six lines) and 44 (seventeenth line) direct additional air (or water) and sulfuric acid into the ferric sulphate reactor 3 8 · according to the reaction formula (3) 4FeS04+2H2S04+02 =2Fe2(S04)3+ 2H20

Therefore, the reaction of ferrous sulfate and sulfuric acid with oxygen can be carried out to produce iron sulfate (second sulfuric acid compound), and the working temperature is about 2 to 3 degrees Fahrenheit, and the iron sulfate formed is formed. The aqueous solution concentration was 43 w·t. %. In this preferred embodiment, the reaction is controlled to operate at a temperature of 18 degrees Fahrenheit and one atmosphere. In addition, in this step, the role of the introduced air is mainly to provide oxygen during the reaction, so the pipeline 42 may also directly cite a reactive substance such as oxygen and ozone. When the amount of sulfuric acid added is less than the value of the chemical equilibrium dose, iron sulfate forms a polymer compound. When the amount of sulfuric acid added is just maintained at a chemical equilibrium dose, the sulfuric acid reacts with the ferrous sulfate to react. The concentration of sulfuric acid in the device 38 is reduced, thereby preventing the precipitation of ferrous sulfate, and the tile further prevents the final product from having excessive free acid and reducing the final yield.

Page 13

1257919 . ------ Case No. 91imifi Year of the month 攸 5, invention description (10) "~' "-- the content of ferrous sulfate. Therefore, the ratio of sulfate ion to iron ion needs to be monitored and Control, so that the oxidation reaction can reach a complete reaction, so that the final product = iron sulfate does not contain excessive sulfuric acid or free sulfuric acid. According to the experimental data of the present invention, the ratio can be between 丨·8 and 丨·3, and The effect of 1 · 5 is optimal. The reactants in the ferric sulfate reactor 38 will flow through a line 46 (the tenth line), and after passing through the pressurization procedure of the pump 48, it is circulated through a heat exchanger. 50, and the heat exchanger 5 can be heated to about 18 degrees Fahrenheit by means of a steam sleeve or directly by steam heating, so that the ferric sulphate reactor 38 does not need to be equipped with other heaters. The substance in the device 50 sends about 43% of the concentration of ferric sulphate to the ferric sulphate storage tank 5 via line 52. At this time, not all of the ferric sulphate is sent to the ferric sulphate storage tank 53 with some products and others. The reactants will pass through the official line 54 (the thirteenth tube) And 56 are refluxed to the ferric sulphate reactor 38. To divert the reactants fed to the reactor 38 and the storage tank 53, a splitter (not shown) may be added. The loops are sent back via lines 54 and 56. The ferric sulphate will act through a mixing nozzle 57 present in the reactor 38 to achieve complete thorough mixing of the reactants in the reactor 38. The sulphuric acid in the reactor 38 is returned to the reaction is 3 8 due to the return of the ferric sulphate to the reaction The iron residence time will increase relatively 'this increases the conversion rate of ferrous sulfate to ferric sulphate, so the iron sulphate, one of the final products, has a high purity quality, such as the output of pipeline 52. It contains about 12% of the ferric ion solution. The air will also be guided into the ferric sulphate reactor 38 by a line 58 (fourteenth line) at a certain rate, and the injected air will be supplied in addition to

Page 14 1257919 -~ --Ά 91113316_年月日日改五、发明说明(11) In addition to the oxygen required for the oxidation of valence iron into ferric iron, it can be used as a mixture and agitation for the reactants. It is interconnected with the return line 54, so that the 'line 54, 54 can also replace the line 42 for conveying air, or the line 42 can serve as a line for conveying water. Line 54 can also have a mixing nozzle (e.g., 57; not shown) so that air can more assist the reactants in reactor 38 to perform the desired action. The air from the ferric sulphate reactor 38 is sent to a scrubber 6〇5 via line 60 before being released to the atmosphere, where it is released after being cleaned, so that it does not cause a defect in the atmosphere. In order to improve the variability of the present invention, the pipeline 4 is further connected to a heat exchanger 7 by a line 71 (fifteenth pipeline), and the heat + parent converter 70 is further passed through a Line 7 2 is connected to a ferrous sulfate storage tank 73. Thus, the ferrous sulfate produced by the separator 34 can be directly recovered through the heat exchanger 7 and placed in the ferrous sulfate storage tank 73, and it is not necessary to completely produce the iron sulfate recovery. Of course, since the heat source of the ferrous sulfate product is not so important, the line 71 can also be directly connected to the ferrous sulfate storage tank 73 without the need for a further heat exchanger 7 〇. If the batch process is used in the manufacturing process, the feeding procedure is first

After entering the water and sulfuric acid to the reactor 38, and after the reactor 38 is filled with water and sulfuric acid, the ferrous sulfate produced by the reaction of the gluten solution is added to the anti-deer crying 3 8 as in the continuous operation procedure. In general, the same similar purpose and result can be achieved. In addition, if the waste acid solution to be treated is from a zinc electroplating plant, the solution reaction is 10, and sulfuric acid is added to replace the gas ion, then a mixture of ferrous sulfate/zinc sulfate is precipitated, and sulfuric acid is passed through line 32. Ferrous/zinc sulfate 1257919 V. INSTRUCTION DESCRIPTION (12): The sputum and water are introduced into the separator 3 from the solution reaction state 10, although ferrous sulfate and zinc sulfate are easily dissolved in the hot sulfuric acid aqueous solution, The solubility of the mouth will decrease greatly with the increase of the amount of sulfuric acid. This property uses this property to separate the ferrous sulfate and zinc sulfate from sulfuric acid and water. As long as the concentration of sulphur in the solution reactor is constant. Value: 2 ° = application: 59 ".%, the ferrous sulfate / zinc sulfate mixture in the concentration of sulfuric acid" If the more precise control, the formation of crystal grains and the characteristics of filtration will be better. here . The substance is in the form of a mixed slurry, the mud-like substance = benefit 34, the ferrous sulfate/zinc sulfate mixture is selected from the sulfuric acid and water 2: centrifugal separator, filter, cyclone, sedimentation tank or any# The other one is applicable as long as the detachable device is applicable. Cry 10 minutes of sulfuric acid and water will be refluxed through the line 36 to the solution reaction 10, the sulfuric acid reflux design will increase the chemical reaction formula (1) and (2), the sulfuric acid molecules required in the reaction process, and thus reduce the Need to add:: squash, quantity. In the case of batch operation, the supplemental sulfuric acid may be added during the reaction process or periodically, however, the sulfuric acid concentration f must be precisely controlled, so that a good quality can be obtained in the subsequent process towel. Commercially valuable recycled product. The ferrous sulfate is directly precipitated from the separator 34, and is separated from the zinc mixture, which are all reacted by the reactor iron (four), and the subsequent processes are as described above. In addition, after separation of the separation process, an organic solution number 91113316 1257919 is utilized.

V. Inventive Note (13) The zinc ion can be separated from the ferrous sulfate to form a ruthenium. * The organic compound containing the deionized ion is separated and guided to the zinc sulfate reducer 615. : The aqueous solution of sulfuric acid or salt present in the sulfuric acid reducing hexahydrate is removed, so that zinc sulfate can be produced (the third sulfated character is separated, which is the third step of the invention. Part of the ') agent will be cooled from the zinc sulfate via line 63 (the third line) and sent to the separator 34' and can be reused. The aqueous solution of sulfuric acid reaches a cooler 64 and is cooled. The sulphuric acid word is presented as the surname of the second sorrow, and the sulphuric acid is removed from the pipeline 62 (the eighth pipeline) to the zinc sulphate and the sulphate is 70% recycled. In particular, the cooler 64 can also be used if it is not used. After that, ~,, the claws of the fresh, Chen Yu bath through the truck or railway traffic

The tool is shipped out to carry it back to you / ^田_ . . A by - line m (the third tube - 匕3 acid zinc reducer 615 acid aqueous solution or hydrochloric acid. According to the present invention, there are many variations, such as providing a reaction, which is designed to the iron sulfate reactor 38 to stay in the reactor. At the time of the stay, it is also said that the solution reactor and the iron sulfate are all treated with zinc chloride; of course, the foregoing embodiment 1 is applicable to other ^#>^::^ according to the inventive spirit of the present invention. The above description is only in the liquid 'for example, the material of the invention. The best embodiment of the invention is only one of the two inventions, and 1257919 is the number of 911113316. The fifth embodiment of the invention (14) is not intended to limit the scope of the practice of the present invention. The invention is also susceptible to various modifications and changes in the form, structure, characteristics and spirit of the invention as claimed in the appended claims.

Figure No. Description 10 Solution Reactor 12 Line 13 Line 14 Line 16 Absorption Tower 18 Line 19 Line 20 Heat Exchanger 21 Line 22 Line 225 Hydrochloric Acid Collection Tank 24 Line 26 Line 28 Blowing Equipment 32 Line 34 Separator 36 Line 38 Sulfuric Acid Iron reactor 40 Line 42 Line 44 Line 46 Line 48 Pump 50 Heat exchanger 52 Line 53 Ferric sulfate storage tank 54 Line 56 Line 58 Line 60 Line 605 Washer 61 Line 615 Iron sulphate restorer 617 Line 62 Line 6 2 5 Zinc Sulfate Collection Tank第18页

1257919 BRIEF DESCRIPTION OF THE DRAWINGS Case No. 91113316 曰 Revision 1 FIG. 1 is a schematic configuration of a preferred embodiment of the present invention.

Claims (1)

1257919 I-_Case No. 9111 along the 16th day of the year ____ VI. Application for patent scope 1 · A method for producing sulfuric acid compounds from a solution containing vapors, the main steps of which include: The spent pickling solution containing a gasified ferrous iron and a gasification gas is introduced into a solution reactor through a first line, and reacted with sulfuric acid present in the solution reactor to become a hydrochloric acid and a ferrous sulfate/ a zinc sulfate mixture, wherein the concentration of sulfuric acid in the solution reactor is controlled between 10% by weight and 98% by weight, and the sulfuric acid is heat treated to between 60 and 300 degrees Celsius; Introducing an air stream into the solution reactor through a second line, and passing the hydrochloric acid gas to the solution reaction state via a third line to an absorption coupling and the air flow rate is 1 2 〇〇c F Μ~1 600CFM is the best; a part of the hydrochloric acid in the absorption tower is introduced into a hydrochloric acid collection tank by a fourth pipeline, and is recycled; The sulfuric acid reacted by the ferrous sulfate in the solution reactor is separated from the zinc ion by an organic solvent through a sixth tube to be an organically introduced into the zinc sulfate reducer via a seventh line. Zinc and the organic solvent; / zinc sulphate mixture and no wire introduction into a separator; ferrous sulfate / zinc sulphate mixture, and the organic compound zinc sulphate in the reducer, and reacted with the deposit, to produce The zinc sulfate is introduced into the acid-sulphate zinc storage tank through an eighth pipeline - and is recycled; the ferrous sulfate is separated from the ferrous sulfate/zinc sulfate mixture, and borrowed Page 21---------- 1257919 Case No. 9113331R Year_I Amendment_ VI. Patent application scope is introduced into a ferric sulfate reactor by a ninth pipeline; and ferrous sulfate is present in iron sulfate The reaction of the sulphuric acid and an air reaction is carried out to become a product of iron sulphate, which is then introduced into a ferric sulphate collection tank via a tenth line and recycled. 2. The production method according to claim 1, wherein the sulfuric acid present in the solution reactor is controlled to be introduced into the solution reactor by an amount and concentration in an eleventh line. 3. The production method according to claim 1, wherein the reaction temperature present in the solution reactor is preferably 180 degrees Fahrenheit. 4. The production method according to claim 1, wherein the concentration of sulfuric acid in the solution reactor is preferably 5.9 % by weight. 5) The production method as described in claim 1 may further comprise the following steps: providing a stirring device in the solution reactor, wherein the stirring device continuously performs the waste acid solution and the sulfuric acid in the solution reactor. Stir the action to accelerate the reaction. 6. The production method according to claim 1, which may further comprise the following steps: refluxing the unrecycled hydrochloric acid in the absorption tower into the solution reactor by the air stream and a fifth line. 7 · If the output method described in item 6 of the patent application scope, the following steps may be included 1257919 Case No. 91113316 Amendment VI, the patent application scope is connected with an air blower on the fifth pipeline, and the air flow of the air blower of the air blower is actuated to accelerate the accelerated reflux of hydrochloric acid in the fifth pipeline into the solution reactor. . 8. The method of producing according to item 7 of the patent application, wherein the third line system can be combined with the fifth line. 9. The production method according to claim 1, wherein the water can be introduced into one of the third line, the absorption tower and a combination thereof to control the concentration of hydrochloric acid entering the absorption tower. I 〇 · The production method described in item 1 of the patent application, which exists in The concentration of hydrochloric acid in the absorption tower is between 19% and 24% by weight. II. The production method according to claim 1, wherein the fourth pipeline is further provided with a heat exchanger, which can be used for cooling the hydrochloric acid to be recovered to a certain temperature, and the certain temperature is Fahrenheit 6 〇 to 1 2 0 degrees. 1 2 The production method according to the first aspect of the patent application, wherein the temperature of the hydrochloric acid to be recovered by the heat exchanger is preferably 11 degrees Fahrenheit. 13) The method of producing according to claim 1, wherein the separation is one of a centrifugal separator, a filter, a cyclone, a sink, and a combination thereof. 1 4 · The production method as described in claim 1 of the patent application may further include - the following steps: sulfuric acid and water separated by the separator may be refluxed to the solution via the tenth-line Inside the reactor. Page 23 1257919 --j No. 91113, m VI. Patent Application No. 15 == The production method described in claim 1 of the patent application, wherein the organic bath is a carrier D2EHPA, 801 and a combination thereof. Among them. A ' mouth, as described in the patent application scope, can also include the following steps: by connecting a cooler on the eighth line, it can be used to cool the zinc sulfate passing through, so that the zinc sulfate is presented. Crystalline form. The production method according to claim 1, wherein the working temperature in the ferric sulphate reactor is maintained between 1 20 and 3 0 degrees F 16 16 18 18 as in the patent scope iron reactor The best work. 1 9 · If the scope of the patent application is the best, the output of the iron reactor is the best. 2 0 · If the following steps are applied to the ferric sulphate by a connection to the ferric sulphate at 120 degrees to 300 degrees, the thirteenth tube 21 can be used. The production method is as follows: the soil system is at a pressure of one atmosphere, and the production method described in the first item of the first embodiment is controlled by the concentration of the aqueous solution of the ferric sulfate, wherein the sulfuric acid is 180 degrees, wherein the sulfuric acid is 43% by weight. The production method described in the item may further include a heat exchanger having ten pipelines, which may be used for a certain degree of overflow, and the certain temperature system may be between Fahrenheit, and part of the ferric sulfate may be passed through the tenth tube and the line. The storage tank is recovered, and a portion of the carbonic acid _ I line is returned to the ferric sulphate reactor. % of the output method described in item 20, which may include % Page 24 1257919 ------ Case No. 9113331丄__Main Month J__ 正正-- VI. Application for Patent Range The following steps are carried out by a fourteenth pipeline connected to the thirteenth pipeline. An air flow is passed through the thirteenth line to the ferric sulphate counter. 22. The method of producing according to claim 2, wherein the air flow present in the fourteenth line is one of air, oxygen, ozone, and a combination thereof. 23. The production method as described in claim 2 of the patent application may include the following steps: d. A mixing nozzle is connected to the ferric sulphate reactor at the end of the thirteenth line. 24. The production method as described in claim 1 of the patent application may further comprise the following steps: the sulfuric acid and the air system present in the ferric sulphate reactor are respectively connected to the tenth of the ferric sulphate reactor by a corresponding one. The six-pipeline and the seventeenth pipeline' are controlled to control the sulfuric acid concentration and the air-gas flow from the outside. 25 The production method as described in claim 1, wherein the amount of sulfuric acid present in the ferric sulfate reactor is Maintaining the chemical equilibrium dose value 〇26 · The production method described in claim 1, wherein the amount of sulfuric acid present in the ferric sulphate reactor is slightly lower than the chemical equilibrium dose value Ο 27 · as claimed in the patent scope The production method according to item 1, wherein the sulfuric acid 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 5 。 Preferably, the ratio of sulfate ion to iron ion in the ferric sulphate reactor is preferably 1.5. 2 9 · The production method as described in claim 1 of the patent application may further comprise the following steps: by means of a scrubber connected to the ferric sulphate reactor, it is possible to wash the effluent discharged from the ferric sulphate reactor gas. 30. According to the production method described in claim 1, the following steps may be included: the ferrous sulfate separated by the separator may be separated by a fifteenth pipeline connected to the ninth pipeline. Introduced into a ferrous sulfate storage tank 〇 3 1 · The production method described in claim 30 of the patent application may include the following steps by a heat exchanger connected to the fifteenth pipeline, It can be used to control the passing ferrous sulfate between 120 degrees and 300 degrees Fahrenheit. 3 2 . The method of production of claim 1, wherein the excimer may also be an aluminum ion. 3 3 · A production device for producing a sulfuric acid compound from a solution containing chloride, the main structure of which comprises: a solution reactor for setting a sulfuric acid and a waste containing a chloride therein Pickling the solution and letting it react to produce a sulfuric acid Page 26 1257919 Case No. 91113316 ± _a 4 曰 Amendment __ 6. Patented compound and hydrochloric acid; an absorption tower connected to the solution reactor by a third line, which can be used to place the reactor from the reactor a hydrochloric acid collection tank; connected to the absorption tower by a fourth line, which can be used for recovering part of hydrochloric acid from the absorption tower to be recovered; a separator, and a solution by a sixth line The reactor is connected and is capable of placing one of the sulfuric acid compound and the unreacted sulfuric acid produced from the solution reactor; a second sulfuric acid compound reactor is connected to the separator by a ninth line, and is placed from the reactor a first sulfuric acid & compound in the separator, and reacting the first sulfuric acid compound to produce a second sulfuric acid compound; and a second sulfuric acid compound storage tank, by a tenth pipeline a plant, an acid compound reactor connection, which can be used to recover a portion of the second sulfuric acid to be recovered from the second sulfuric acid compound reactor, 34 35 36 The outputs of the first enclosure 3 3 Γ / \ &. I-based compound is ferrous sulfate. Such as the scope of the patent patent q q The sulfuric acid compound is the production device described above, and the second is the top of the patent application. a third sulfuric acid compound, the production device, may also include an off-machine connection, and the original device, with a seventh pipeline and the sub-compound; 'to be placed from the separator Third acid breaking 1257919 9111331B VI. Application for Patent Range Amendment 37 38 39 40 A third sulfuric acid compound You 4 Trisulfuric acid compound:: The tank ' is connected to the third third sulfated person by: an eighth line, which can be used for recycling Processing the third sulfuric acid compound from the α-reactor to be recovered, such as the patent application scope 箸q ρ π to visit the production device described by the child 3 from the birth of the brothers, wherein the third sulfuric acid compound is optional# & + ^ Λ ^ ^, selected as zinc sulfate, sulfuric acid | Lu and its one of the beans. The production device described in item 33 of the ί 申 利 范围 范围 range, the absorption in the # can still be connected to the solution reactor by the fifth line, and the hydrochloric acid in the absorption tower that is not sent to the hydrochloric acid collection tank can be obtained. If the product is returned to the solution reactor, such as the production device described in claim 38, wherein the fifth pipeline can be connected with an air blower. Wherein the fourth official line can be equipped with a heat exchanger, and the heat exchanger can be connected to the absorption tower by an eighteenth pipeline, and the hydrochloric acid that has not been sent to the hydrochloric acid collection tank for recovery can be refluxed to the absorption. 41. The production device according to claim 33, wherein the third official line is provided with a nineteenth pipeline that can introduce water into the absorption tower. 42. The production device according to claim 33, wherein the separation is connected to the solution reactor by a twelfth line, and the excess sulfuric acid and water present in the separator are returned to the reactor Solution reactor Page 28 1257919 Page 29 1257919 52 · 53 · Sulfuric acid compound; ^ μ, crying, 廿..., the original hunting is connected by a 19th pipeline to the separated di-branched to reflux the organic solvent present in the third sulfuric acid compound reducer to Inside the separator. There is a production device according to the scope of claim 36, wherein a cooler can be installed on the occupant line. a method for producing a sulfuric acid compound from a solution containing a vapor, the main steps of which include: a waste acid pickling solution having a gasified ferrous iron via a first line and a solution reaction And reacting with sulfuric acid present in the solution reactor to become monohydrochloric acid and ferrous sulfate, and the concentration of sulfuric acid in the solution reactor is controlled to be from 1% by weight to 98% by weight. Between the amount 'and the sulfuric acid is heat treated to between 6 华 3 〇〇 3 degrees; an air stream is introduced into the solution reactor through a second line, and the hydrochloric acid is passed through the air stream The three lines are taken away from the solution reactor to an absorption tower, and the air flow rate is preferably 丨20〇CF Μ~1600 CFM; a portion of the hydrochloric acid in the absorption tower is introduced into the hydrochloric acid collection tank by a fourth line. And recycling the ferrous sulfate and unreacted sulfuric acid in the solution reactor through a ninth line into the ferric sulphate reactor; and ferrous sulphate and one of the sulphuric acid present in the ferric sulphate reactor An air reaction to become a product of iron sulphate, which in turn introduces a portion of the ferric sulphate into the iron sulphate collection tank via a tenth line, and Page 30 1257919 Case No. 91113316 修正 Amendment 6. The scope of application for patents shall be recycled. 5 4 . The production method as described in claim 5, which may include the following steps: introducing ferrous sulfate in the solution reactor into a ferrous sulfate storage tank via a ninth line. Page 31 1257919 Case No. 91113316 Λ_a Amendment Page 3