KR20170013065A - Method for manufacturing calcium phosphate powder fertilizer using waste etching solution of semiconductor - Google Patents

Abstract

The present invention relates to a method for preparing a fermentation product comprising 50% to 75% by weight of a phosphorus acid solution; And 25 wt% to 50 wt% of a reactant comprising at least one of quicklime and desulfurized gypsum; Is added to a reactor and reacted at a stirring speed of 10 rpm to 30 rpm for 3 minutes to 15 minutes to prepare a powdery fertilizer having an average particle diameter of 0.1 to 30 mm, Which is capable of recycling industrial by-products, increasing the content of water-soluble calcium phosphate in the produced fertilizer, effectively preventing the irritating odor of nitric acid and acetic acid, providing a calcium phosphate powder A fertilizer production method can be provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing calcium phosphate powder fertilizer by using a semiconductor manufacturing < RTI ID = 0.0 > liquor. ≪ / RTI >

The present invention relates to a method for producing calcium phosphate powder fertilizer using a semiconductor manufacturing by-product liquid.

The semiconductor manufacturing process (or the display substrate manufacturing process) includes an etching process in which a semiconductor thin film (or a thin metal film) is etched using an acidic chemical to process the semiconductor thin film into a desired shape. After this etching process, an etching waste solution containing a large amount of acidic substance is produced as a by-product.

In recent years, as the amount of etching waste generated along with the growth of the semiconductor industry has increased, environmental pollution and disposal costs associated with disposal have become a heavy burden. Phosphoric acid, which occupies the majority of the etching waste solution, is an expensive chemical. Since acetic acid, nitric acid, etc. are industrially useful materials having various uses, recently, a recycling method of an etching waste solution has been actively developed.

As a method of recycling the above etching waste solution, there is a method of producing nitric acid fertilizer or phosphoric acid fertilizer from an etching waste solution. For example, in Patent Document 1 (No. 10-1157570, "Method for Producing Calcium Triphosphate Using Mixed Waste Acid Generated in a Liquid Crystal Display Device Manufacturing Process"), the mixed waste acid solution is subjected to vacuum evaporation treatment, A primary vacuum evaporation step of removing acetic acid; A diffusion dialysis treatment step of subjecting the remaining liquid after the first vacuum evaporation treatment to diffusion dialysis treatment to remove aluminum components; A second vacuum evaporation step of concentrating the phosphoric acid by the vacuum evaporation treatment after the diffusion dialysis treatment; Reacting the concentrated phosphoric acid with calcium carbonate, filtering the mixture, and adding the calcium hydroxide solution to the resulting filtrate to obtain a neutralized reaction solution; Subjecting the reaction solution to a temperature and humidity of 40-50 캜 and a humidity of 80-90% for 7-12 hours to prepare a calcium triphosphate slurry; And a step of drying, calcining and pulverizing the water of the calcium tripotassium carbonate slurry to prepare calcium triphosphate using an LCD mixed waste acid.

However, such a method has a problem in that it requires high fuel cost required for heating, high maintenance cost due to complicated machinery and equipment, low cost efficiency, and low water-soluble calcium phosphate content, There is a problem.

Patent Document 1: Korean Patent No. 10-1157570

It is an object of the present invention to provide a process for producing a phosphorus-containing phosphorus acid solution (etching waste solution) containing phosphoric acid, nitric acid and acetic acid, which is generated in a process for producing a semiconductor or a display substrate, And a method for manufacturing calcium phosphate powder fertilizer which is excellent in productivity and economy.

Another object of the present invention is to provide a method of manufacturing a calcium phosphate powder fertilizer which is advantageous in powdering by increasing the content of water-soluble calcium phosphate in the produced fertilizer, effectively preventing irritating odor of nitric acid and acetic acid, I have to.

One embodiment of the present invention comprises 50 to 75% by weight of a by-product phosphoric acid solution containing phosphoric acid, nitric acid and acetic acid generated in the process of manufacturing a semiconductor or a display substrate; And 25 wt% to 50 wt% of a reactant comprising at least one of quicklime and desulfurized gypsum; Is added to a reactor and reacted at a stirring speed of 10 rpm to 30 rpm for 3 minutes to 15 minutes to prepare a powdery fertilizer having an average particle diameter of 0.1 to 30 mm, .

The reactive material includes quicklime and desulfurization gypsum, and the content of the quicklime and the desulfurization gypsum in the reactant may be 12.5 to 30 wt% and 70 to 87.5 wt%, respectively.

The method may further include introducing zeolite in the reaction of the composition, wherein the amount of zeolite may be 5 parts by weight to 10 parts by weight based on 100 parts by weight of the total composition.

The calcium phosphate powder fertilizer production method may further include feeding the powdery fertilizer to a rotary drum cooler using an intermediate storage hopper and a conveyor, and then cooling the powdery fertilizer for 10 minutes to 60 minutes.

The phosphorous phosphoric acid solution may include 60 to 75% by weight of phosphoric acid, 1 to 5% by weight of nitric acid, 5 to 15% by weight of acetic acid, and 15 to 20% by weight of water.

Disclosure of Invention Technical Problem [10] The present invention provides a calcium phosphate powder which is capable of recycling industrial by-products, enhances the content of water-soluble calcium phosphate in the produced fertilizer, effectively prevents irritating odor of nitric acid and acetic acid, A fertilizer production method can be provided.

1 is a schematic view illustrating a manufacturing method according to an embodiment of the present invention.
2 is a photograph of the calcium phosphate powder fertilizer prepared in Example 1 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Throughout this specification, the same or similar components are denoted by the same reference numerals. In the following description, well-known functions or constructions are not described in detail since they would obscure the invention in unnecessary detail.

One embodiment of the present invention comprises 50 to 75% by weight of a by-product phosphoric acid solution containing phosphoric acid, nitric acid and acetic acid generated in the process of manufacturing a semiconductor or a display substrate; And 25 wt% to 50 wt% of a reactant comprising at least one of quicklime and desulfurized gypsum; Is added to a reactor and reacted at a stirring speed of 10 rpm to 30 rpm for 3 minutes to 15 minutes to prepare a powdered fertilizer having an average particle diameter of 0.1 to 30 mm .

1 is a schematic view illustrating a manufacturing method according to an embodiment of the present invention. Referring to this, the method for producing calcium phosphate powder fertilizer of the present invention comprises a solution of phosphorus acid phosphate (etching waste solution); And a reactive material containing at least one of quicklime and desulfurized gypsum, are weighed in respective titration contents, and then put into a reactor as a composition (100).

The phosphorus acid phosphate solution in the composition is not limited as long as it contains phosphoric acid as an etching waste solution generated as a by-product in the industrial field. Specifically, it may be an etching waste solution containing phosphoric acid (hereinafter referred to as " Pusan Phosphoric Acid Liquid ") generated in a semiconductor manufacturing process or a display substrate manufacturing process. In this case, since the waste liquid containing phosphoric acid and the like can be recycled as a fertilizer, the waste liquid can be recycled as fertilizer, which not only has high economic efficiency, but also can be converted into an organic material because it is used as fertilizer. The kind of the semiconductor or the kind of the display substrate is not limited.

For example, the Pb phosphoric acid solution may include 60 to 75% by weight of phosphoric acid, 1 to 5% by weight of nitric acid, 5 to 15% by weight of acetic acid, and 15 to 20% by weight of water. In this case, the content of phosphoric acid is higher than that of nitric acid, which can serve as a suitable source of phosphoric acid for the production of calcium phosphate fertilizer. Further, it is possible to additionally supply a nitrogen source to the calcium phosphate fertilizer while preventing the occurrence of irritating odor by nitric acid.

The reactive material in the composition is a compound containing a calcium component, including burnt lime; Desulfurized gypsum; Or a mixture of quicklime and desulfurized gypsum. These reactants can react with nitric acid, phosphoric acid, and acetic acid in the phosphorus acid solution to produce calcium nitrate, calcium phosphate, and calcium acetate. The above-mentioned calcium nitrate, calcium phosphate and calcium acetate are included in the fertilizer and act as a main source of nitrogen and phosphoric acid.

The quicklime contains calcium oxide as a main component, and may also include other minerals or impurities which are generally included in quicklime. For example, calcium oxide (CaO) may be contained in an amount of 85% by weight to 100% by weight, for example, 85% by weight to 96% by weight of the whole quicklime. Within this range, it is possible to provide a calcium phosphate powder fertilizer producing method excellent in calcium nitrate and calcium phosphate producing ability.

In one embodiment, the quicklime may be one having a water content of 0%. In this case, the quicklime can be prevented from being hydrated and changed into the slaked lime before the reaction, thereby further improving the reactivity.

The desulfurization gypsum contains calcium sulfate as a main component and may also include other minerals or impurities which are generally contained in the desulfurization gypsum. For example, 15% to 100%, such as 15% to 85% by weight calcium sulfate in the total desulfurization gypsum, specifically 60% to 85% by weight quicklime and 15% to 40% % By weight may be used. The desulfurized gypsum acts as a sulfur source of fertilizer, and can maintain the content of nitrogen element in the fertilizer and prevent the generation of irritating odor by nitric acid. Sulfur-containing fertilizers can be used as fertilizers for special crops that synthesize sulfur in plants.

In one embodiment, the desulfurized gypsum may have a water content of 0%. In this case, the lime component, which may be partially contained in the desulfurized gypsum, is prevented from being hydrated and changed into the slaked lime before the reaction, thereby further improving the reactivity.

In particular, desulfurized gypsum plays an important role in improving the content of water-soluble calcium phosphate. Examples of the calcium phosphate include tricalcium phosphate (hereinafter referred to as "usable calcium phosphate") and calcium hydrogen phosphate (hereinafter referred to as "water-soluble calcium phosphate"). When the desulfurized gypsum is used as the reactant, the content of the water-soluble calcium phosphate, which is difficult to increase in content by the conventional method, can be improved as in the calcium phosphate powder fertilizer manufacturing method of the present invention.

Specifically, although conventional calcium phosphate can be produced by the conventional method for producing phosphoric acid fertilizer, it is not easy to produce water-soluble calcium phosphate. Existing calcium phosphate can act as a source of phosphoric acid in soils where acidic soil or organic acids generated from microorganisms are present, whereas water-soluble calcium phosphate can be easily applied as a phosphate source by water after being fed to the soil, Speed is excellent.

More specifically, when a desulfurized gypsum is used as a reactant as in the present invention, an excel- lent calcium phosphate is produced with high efficiency by a reaction between a desulfurized gypsum and phosphoric acid. Thereafter, the liberated sulphate of the desulfurized gypsum is reacted with moisture and the prepared exfoliating calcium phosphate, so that the water-soluble calcium phosphate can be produced.

Further, the sulfuric acid component contained in the desulfurized gypsum can act on the nitric acid component in the phosphorus acid solution to promote the crystallization of the nitric acid component during the reaction. In this case, the desulfurized gypsum can prevent the irritating odor generated by the volatilization of the nitric acid component while increasing the nitrogen element content in the fertilizer.

The desulfurized gypsum can be produced, for example, by burning a mixture of 30 to 70 wt% of limestone and 30 to 70 wt% of petroleum coke at 800 to 900 DEG C in a fluidized bed combustion boiler of a petroleum refining process, The desulfurizing gypsum can be a desulfurization gypsum produced in the course of mixing the gypsum. The production method using such a desulfurized gypsum as a reaction material can further improve the content of the water-soluble calcium phosphate and the orofic acid calcium phosphate in the produced fertilizer and improve the rate at which the fertilizer acts on the soil.

The reactant may be used in the form of a particle or a powder. In this case, the reaction rate can be controlled more gently than in the case of being used in the liquid phase, thereby preventing the reaction from occurring rapidly. Generally, the reaction force of nitric acid, phosphoric acid and acetic acid contained in the phosphorus acid solution is the order of nitric acid> phosphoric acid> acetic acid. In this case, since the reaction force of nitric acid is the highest, when potassium nitrate is rapidly added to a nonuniform phase, calcium phosphate may be produced when the reactant is added. On the other hand, when the reaction rate is moderately controlled as in the present invention, the mixing uniformity of calcium nitrate and calcium phosphate in the prepared fertilizer can be improved. In addition, when a particulate or powdery reaction material is used, it is possible to omit the pulverization process of the liquid form, the slurry form, and the cake form, so that the production process is simple and the productivity is excellent.

In one embodiment, when using only quicklime as the reactant, the content of quicklime may be, for example, from 25 wt% to 50 wt% of the total composition. Within the above range, it is possible to provide a calcium phosphate powder fertilizer which is advantageous in controlling the reaction heat and does not generate nitric acid and acetic acid odor.

In other embodiments, when using only desulfurized gypsum as the reactant, the content of desulfurized gypsum may be, for example, from 35% to 50% by weight of the total composition. Within the above range, it is possible to provide a calcium phosphate powder fertilizer which is advantageous in controlling the heat of reaction, has high content of water-soluble calcium phosphate, and does not generate nitric acid and acetic acid odor.

In another embodiment, the reactants can use mixtures of quicklime and desulfurized gypsum. In this case, the content of quicklime in the reaction material may be 12.5 to 30 wt%, and the content of desulfurization gypsum may be 70 to 87.5 wt%. Within the above range, it is possible to provide a calcium phosphate powder fertilizer which is excellent in productivity, has an excellent control of the heat of reaction, has a high content of water-soluble calcium phosphate and / or exfoliating calcium phosphate and does not generate nitric acid and acetic acid odor.

The composition comprises 50% by weight to 75% by weight of the phosphorus acid solution in the total composition and 25% to 50% by weight of the reactant. Within the above range, it is possible to provide a calcium phosphate powder fertilizer which does not generate nitric acid and acetic acid odor.

A zeolite may be added during the reaction of the composition. In this case, not only the irritating odor can be further reduced, but also the quality of the fertilizer can be further improved. The amount of the zeolite may be 5 to 10 parts by weight based on 100 parts by weight of the total composition. Within the above range, the workability is excellent, the viscosity is easily controlled, and the effect of improving the quality of the fertilizer can be excellent.

The order of addition of the phosphorus acid solution and the reactant is not limited. For example, the phosphorus acid solution may be added while stirring the reaction material after the reactant is first introduced into the reactor. In this case, the reactivity can be improved and the uniformity of the produced reactant can be further improved.

The reactor into which the composition is injected may be, for example, a reaction mixer including a stirring blade. In this case, the stirring speed and the average particle diameter of the product to be produced can be uniformly controlled.

In one embodiment, the method for producing calcium phosphate powder fertilizer can be carried out by adding a phosphorus acid solution (etching waste liquid) while keeping the stirring speed at 10 rpm to 30 rpm after charging the reaction material into the reactor. In this case, the exothermic reaction occurs violently after 1 to 3 minutes from the solution of the phosphorous acid (etching waste solution). At this time, the exothermic reaction temperature can be controlled at 100 ° C to 140 ° C. In this case, nitric acid and acetic acid are partially evaporated together with the water mixed in the Pusan phosphoric acid solution (etching waste solution), thereby removing the nitric acid and acetic acid odor of the prepared calcium phosphate powder fertilizer.

The reaction of the phosphorus acid solution with the reactant in the reactor is carried out for 3 to 15 minutes. Within this range, the control of the reaction heat is advantageous, and it is advantageous to control the average particle diameter of the produced product to 0.1 mm to 30 mm.

The calcium phosphate powder fertilizer manufacturing method further comprises the step of transferring the powdery powder prepared as described above to the intermediate storage hopper 200 and then conveying it to a rotary drum cooler using a conveyer to cool the powdery cake for 10 minutes to 60 minutes can do.

In one embodiment, the powder phase prepared as described above may be transferred (200) to the intermediate storage hopper through the exit gate of the reaction mixer. Subsequently, the powder phase is continuously transferred through a fixed amount discharge conveyor to a rotating drum cooler of 1 rpm to 6 rpm in a rotary kiln form, and cooled (300) for 10 to 60 minutes sufficiently. In this case, a powder fertilizer having an average particle size within the range of 0.1 mm to 30 mm can be prepared and used as a calcium phosphate powder fertilizer raw material in a compound fertilizer manufacturing plant.

In addition, the calcium phosphate powder fertilizer manufacturing method may include discharging the pollutants generated in the manufacturing process to the condenser and the purifier so that the pollutants may be removed to the atmospheric release allowance level (400) and discharged to the atmosphere .

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents which are not described below can be sufficiently technically inferred by those skilled in the art, so that the description thereof will be omitted.

Example  One

A phosphorus acid solution (etching waste solution) and particulate quicklime (CaO 85% content) composed of phosphoric acid (67 wt%), nitric acid (4.5 wt%), acetic acid (9.5 wt%) and water (19 wt%) were prepared.

235 g (47% by weight of the composition) of the quicklime was weighed, then charged into a reaction mixer equipped with a stirring blade, and then maintained at a stirring speed of 20 rpm. 265 g (53 wt%) of phosphorus acid solution (etching waste solution) was gradually added to the reaction mixer to adjust the reaction heat to 126 ° C at maximum. After about 1 minute of reaction time, the reaction heat was started to be reduced. After 15 minutes of reaction time, the reaction heat was lowered to 40 ° C to obtain a product having a minimum particle size of 0.1 mm and a maximum particle size of 10 mm.

The components of the product of Example 1 prepared above were analyzed and the suitability of the harmful component fertilizer process standard was confirmed and shown in Table 1.

Item arsenic
(mg / kg) cadmium
(mg / kg) Mercury
(mg / kg) lead
(mg / kg) chrome
(mg / kg) Copper
(mg / kg) nickel
(mg / kg) zinc
(mg / kg) standard 50 5 2 150 300 300 50 900 result 5.35 1.05 Non-detection Non-detection 30.80 177.68 8.20 5.81 Judgment fitness fitness fitness fitness fitness fitness fitness fitness

Example  2

500 g of a total of 500 g of 350 g of the phosphorus acid solution (etching waste solution) (70% by weight of the total composition) and 150 g of calcium oxide (85% CaO content) were prepared.

Example  3

A total of 500 g of 360 g (72 wt%) of phosphorus acid solution (etching waste solution) and 140 g (28 wt%) of quicklime (85 wt% of CaO) were prepared and then the same procedure as in Example 1 was carried out.

Example 4

500 g of a total of 500 g of 56.5 weight% (283 g) of phosphorus acid solution (etching waste liquid) and 43.5 weight% (217 g) of desulfurization gypsum (68% of CaO) as a reactant were prepared and then the same procedure as in Example 1 was carried out.

Example 5

500 g of a total of 500 g of 60 wt% phosphoric acid solution (etching waste solution) (300 g) and 40 wt% of desulfurized gypsum (content of CaO 68%) as a reactant were prepared and then the same procedure as in Example 1 was carried out.

Example 6

A total of 500 g of 65 wt% (325 g) of phosphorus phosphorus acid solution (etching waste liquid), 29 wt% (145 g) of desulfurized gypsum (content of CaO 68%) and 6 wt% of calcium oxide (85 wt% And the same procedure as in Example 1 was carried out except that the maximum reaction heat was controlled at 122 ° C.

Comparative Example  One

A total of 500 g of 380 g (76 wt%) of phosphorus acid solution (etching waste solution) and 120 g (24 wt%) of quicklime (85 wt% of CaO) were prepared and then the same procedure as in Example 1 was carried out.

Comparative Example  2

400 g (80 wt%) of phosphorus acid solution (etching waste solution) and 100 g (20 wt%) of quicklime (85 wt% of CaO) were prepared in the same manner as in Example 1.

Comparative Example  3

50% of calcium carbonate was added to the reactor, and while stirring, 50% by weight of the phosphorus acid solution was added. The pH of the reaction was adjusted to about 3.5, and the reaction was completed by stirring.

≪ Evaluation of physical properties &

The amount of irritant odor and the content of phosphoric acid in the fertilizer prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were analyzed and are shown in Table 2 (unit:%).

1) Evaluation of irritant odor occurrence

The prepared powder fertilizer was placed in a sealed container having a volume of 1 L and then stored at room temperature (25 ° C) for 7 days. After that, only the air inside the sealed container was separated and the degree of volatilization of nitric acid component and the degree of volatilization of acetic acid component were analyzed.

0: Less than 0.1 ppm of nitric acid or acetic acid is detected in the air.

1: 0.1 ppm or more and less than 0.2pmm of nitric acid or acetic acid are detected in the air.

2: 0.2 ppm or more and less than 0.3 pmm of nitric acid or acetic acid were detected in the air.

3: 0.3 ppm or more of nitric acid or acetic acid is detected in air.

2) Analysis of phosphate content of fertilizer

The quality of fertilizer according to Article 18 (2) and (26) of the Fertilizer Control Act and Article 10 (2) and Article 19 (2) of the Enforcement Decree of the Fertilizer Control Act and sampling standards.

division nitrogen Soluble phosphoric acid Adult mountain for children calcium outage Nitric acid odor Acetic acid odor Judgment Example 1 0.35 18.32 36.38 31.06 14 One 0 fitness Example 2 0.40 14.20 48.05 23.52 20.5 One 0 fitness Example 3 0.41 14.90 49.43 22.87 22.1 One 0 fitness Example 4 0.35 20.74 34.77 33.04 14 0 0 fitness Example 5 0.40 22.03 36.93 31.10 15.6 0 0 fitness Example 6 0.37 23.85 40.01 27.60 19.3 0 0 fitness Comparative Example 1 - - - - 24.9 2 2 incongruity Comparative Example 2 - - - - 18.6 3 3 incongruity Comparative Example 3 0.25 6.85 28.32 21.36 4 2 3 incongruity

As can be seen from the above Table 2, the calcium phosphate powder fertilizers of Examples 1 to 6 prepared according to the calcium phosphate powder fertilizer manufacturing method of the present invention were found to have no acetic acid odor. Further, in Examples 4 to 6 containing the desulfurized gypsum as a reactant, the content of water-soluble phosphoric acid was higher and the effect of preventing the odor of nitric acid was more excellent.

On the other hand, as in Comparative Examples 1 and 3, it was found that the powdery fertilizer produced in a composition deviating from the composition and content range of the present invention was not suitable for use as a powdery fertilizer due to excess acetic acid and nitric acid odor .

Claims (5)

50% to 75% by weight of a by-product phosphoric acid solution containing phosphoric acid, nitric acid, and acetic acid generated in the process of manufacturing a semiconductor or a display substrate; And 25 wt% to 50 wt% of a reactant comprising at least one of quicklime and desulfurized gypsum; Is added to a reactor and reacted at a stirring speed of 10 rpm to 30 rpm for 3 minutes to 15 minutes to prepare a powdery fertilizer having an average particle diameter of 0.1 to 30 mm.
The method according to claim 1,
Wherein the reactive material comprises quicklime and desulfurized gypsum, the content of quicklime is from 12.5 to 30 wt%, and the content of desulfurized gypsum is 70 to 87.5 wt%.
The method according to claim 1,
Further comprising introducing zeolite during the reaction of the composition, wherein the zeolite content is from 5 parts by weight to 10 parts by weight based on 100 parts by weight of the total composition.
The method according to claim 1,
Wherein the calcium phosphate powder fertilizer manufacturing method further comprises transferring the powdery fertilizer to a rotary drum cooler using an intermediate storage hopper and a conveyor, and then cooling the calcium phosphate powder fertilizer for 10 minutes to 60 minutes.
The method according to claim 1,
Wherein the phosphorus acid phosphate solution comprises 60 to 75% by weight of phosphoric acid, 1 to 5% by weight of nitric acid, 5 to 15% by weight of acetic acid and 15 to 20% by weight of water. Way.

Images